Porous shaped metal-carbon products

ABSTRACT

The present invention provides a porous metal-containing carbon-based material that is stable at high temperatures under aqueous conditions. The porous metal-containing carbon-based materials are particularly useful in catalytic applications. Also provided, are methods for making and using porous shaped metal-carbon products prepared from these materials.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. application Ser. No. 16/662,914,filed Oct. 24, 2019, which is a division of U.S. application Ser. No.15/132,048, filed Apr. 18, 2016, now U.S. Pat. No. 10,464,048, issuedNov. 5, 2019, which claims the benefit of U.S. provisional applicationNo. 62/247,727, filed Oct. 28, 2015, the entire disclosures of which areincorporated herein by reference.

FIELD OF THE INVENTION

The present invention provides a novel porous metal-containingcarbon-based material, and related methods and compositions. Thematerials are particularly suited for use as catalyst materials.

BACKGROUND

Renewable raw materials such as sugar and its derivatives are attractivefeedstock sources for potential use in the production of commoditychemicals because they are relatively abundant and cheap. Most of thesematerials are water soluble and can be processed in aqueous solutions.These natural materials contain a lot of oxygen which needs to beeliminated during processing. Usually it can be done by catalytichydrogenation which removes extra oxygen in the form of water. Long termcatalyst stability is a necessity for commodity chemical production,meaning that the catalyst must be stable, productive, and selectiveunder commercial reaction conditions for long periods of time.

One of the cheapest and most available catalysts for this kind oftreatment is metal supported on a mineral carrier, which can be used infixed bed applications. However, catalysts supported on mineral carriershave low stability in aqueous media due to slow support dissolution. Aneed, therefore, exists for new materials that can be commerciallyproduced and that are stable in applications requiring use in an aqueousenvironment. Such materials would be useful in catalytic applications,as well as other applications requiring long term use under aqueousconditions.

SUMMARY OF THE INVENTION

In one aspect, the present invention provides a process for preparing aporous, shaped metal-carbon product, the process comprising:

mixing a carbonaceous material with water, a water-soluble organicbinder, and a (first) metal precursor to form a metal-carbon mixture,wherein the metal precursor is a compound selected from the groupconsisting of a metal carbonate, a metal oxide, a metal hydroxide, asalt of a metal acid, a heteropoly acid, a metal carboxylate, a metalcarbide, a metal chloride, a metal amine complex-containing compound, ahydrate thereof, and a mixture of any two or more thereof;

shaping the metal-carbon mixture to form a green, shaped metal-carbonproduct; and

heating the green, shaped metal-carbon product to a carbonizationtemperature to produce a carbonized, shaped metal-carbon productcomprising a plurality of pores.

In another aspect, the present invention provides porous, shapedmetal-carbon products produced by the processes described herein.

In a further aspect, the present invention provides a process forproducing bis-hydroxymethyltetrahydrofuran (BHMTHF) from2,5-bis-hydroxymethylfuran (BHMF), the process comprising:

contacting BHMF with hydrogen in the presence of a hydrogenationcatalyst comprising a porous, shaped metal-carbon product of the presentinvention to produce BHMTHF.

In a still further aspect, the present invention provides a process forproducing a C₃-C₆ diol from a corresponding C₃-C₆ polyol, the processcomprising:

contacting a C₃-C₆ polyol with hydrogen in the presence of ahydrodeoxygenation catalyst comprising a porous, shaped metal-carbonproduct of the present invention to produce a corresponding C₃-C₆ diol.

In another aspect, the present invention provides a process forproducing 1,6-hexamethylenediamine (HMDA) from 1,6-hexanediol (HDO), theprocess comprising:

contacting HDO with an amine in the presence of an amination catalystcomprising a porous, shaped metal-carbon product of the presentinvention to form HMDA.

In a further aspect, the present invention provides a process forproducing glucaric acid from glucose, the process comprising:

contacting glucose with oxygen in the presence of an oxidation catalystcomprising a porous, shaped metal-carbon product of the presentinvention to form glucaric acid.

In a still further aspect, the present invention provides a process forproducing a dicarboxylic acid from an aldaric acid, or salt, ester, orlactone thereof, the process comprising:

contacting an aldaric acid, or salt, ester or lactone thereof withhydrogen in the presence of a halogen-containing compound and ahydroxygenation catalyst comprising a porous, shaped metal-carbonproduct of the present invention to form a dicarboxylic acid.

In yet a still further aspect, the present invention provides a processfor producing 2,5-bis-hydroxymethylfuran (BHMF) from5-hydroxymethylfurfural (HMF), the method comprising:

contacting HMF with hydrogen in the presence of a hydrogenation catalystcomprising a porous, shaped metal-carbon product of the presentinvention to form BHMF.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a novel porous metal-containingcarbon-based material (i.e., products) having desirable properties. Thematerials exhibit certain properties of the metal components from whichthey are prepared. The durable porous materials are particularlysuitable for use as a catalyst, as well as other applications in need ofmechanically strong, metal-containing materials.

In one embodiment, the present invention provides a process forpreparing a carbonized shaped metal-carbon product, the methodcomprising:

mixing a carbonaceous material with water, a water-soluble organicbinder, and a metal precursor to form a metal-carbon mixture, whereinthe metal precursor is a compound selected from the group consisting ofa metal carbonate, a metal oxide, a metal hydroxide, a salt of a metalacid, a heteropoly acid, a metal carboxylate, a metal carbide, a metalchloride, a metal amine complex-containing compound, a hydrate thereof,and a mixture of any two or more thereof;

shaping the metal-carbon mixture to form a green, shaped metal-carbonproduct and

heating the green, shaped metal-carbon product to a carbonizationtemperature to produce a carbonized shaped metal-carbon productcomprising a plurality of pores (i.e., the “carbonization step”).

Applicants have discovered that porous, carbonized, shaped metal-carbonproducts produced by the processes described herein exhibit certainproperties of the metal despite the metal precursor being mixed withother components of the metal-carbon mixture and subsequently carbonizedtogether with these other components. This effect is particularlyapparent when the products are used as catalysts. As a catalyticmaterial, performance was comparable to, if not better than, a catalystprepared by impregnating (and thus depositing metal onto the surfacesof) a mineral oxide-based support with metal, as demonstrated in Example5, hereinbelow.

The examples also demonstrate that metal precursors employed in thepractice of the present invention do not have to be water-soluble toachieve this effect. They may be water-insoluble. One significance of aprocess that can produce a porous, metal-containing, carbon-basedproduct that exhibits certain properties of the metal which can beprepared, not only from water-soluble metal precursors, but also fromwater-insoluble metal precursors, is that much higher metal loadings canbe achieved as compared to metal loadings that are achieved usingstandard processes, such as, for example impregnation processes. This isbecause higher metal loadings can be achieved in a single step withoutchanging the functional form of the support material, which mightotherwise impact accessibility to the pores.

The processes of the present invention enable the incorporation of awide variety of metal types in/onto carbon that would otherwise bechallenging using more commonly used metal precursors such as metalnitrates. While metal nitrates, which are strong oxidants, can be heatedwith mineral oxide materials to impregnate them without consequence,attempting to use the same process to impregnate carbon on a large scalemay be a potentially hazardous endeavor.

In situ reduction of metal precursor to metal during the carbonizationstep for certain metal precursors is an additional advantage of theprocess as it eliminates the need for a subsequent reduction process.Without wishing to be bound by theory, it is believed that during thecarbonization step, the metal precursor may decompose, and in certaincases, be reduced to a metal. The resulting carbonized product exhibitscatalytic activity, as demonstrated by the studies described in theExamples. This suggests that the metal decomposition products are notonly in a catalytically active form, but that they are accessible (i.e.,located on the surfaces (external/internal)) to the reactants.

A further advantage of the processes of the present invention is thatthe product is relatively “clean” with respect to the absence ofpotential contaminants, such as, for example, a halide (when a metalhalide is not utilized as the metal precursor), which might otherwiseneed to be washed out before use in certain applications.

Metal precursors that are employed in the practice of the presentinvention may comprise a variety of metals. The metals may be a basemetal or a noble metal. As used herein, the term “base metal” refers toa metal that is not a noble metal. The term, “noble metal” is usedherein to refer to Ru, Rh, Pd, Ag, Os, Ir, Pt, or Au.

In some embodiments, the metal is selected from groups IV, V, VI, VII,VIII, IX, X, XI, XII, and XIII. In various embodiments, the metal is ad-block metal. Exemplary d-block metals include, for example, Ni, Co, W,Cu, Zn, Fe, Mo, Ni, Rh, Pd, Ag, Os, Ir, Pt, Au, and the like.

In other embodiments, the metal precursor comprises a metal selectedfrom the group consisting of Cu, Pb, Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co,Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb, Rh, Tl, Ru, Rh,Pd, Ag, Os, Ir, Pt, or Au. Often, the metal precursor comprises a metalthat is a base metal. In specific embodiments, the metal precursorcomprises a metal selected from the group consisting of Cu, Pb, Ni, Zn,Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge, V, Ga,Hf, In, Nb, Rh, and Tl. In some embodiments, the metal precursorcomprises a metal selected from the group consisting of Ni, Co, Mo, Nb,and W. Often, the metal precursor comprises a metal selected from thegroup consisting of Ni and W.

The processes of the present invention can employ a variety of types ofmetal precursors, including a metal carbonate, a metal oxide, a metalhydroxide, a salt of a metal acid, a heteropoly acid, a metalcarboxylate, a metal carbide, a metal chloride, a metal aminecomplex-containing compound, as well as hydrates thereof and mixtures ofany two or more thereof. As explained above, the metal precursor may bewater-soluble or water-insoluble. As used herein the term“water-insoluble” when used in connection with the metal precursor,refers to a metal precursor having a solubility of less than 0.1 wt % inwater. The term “water-soluble”, when used in connection with the metalprecursor, refers to a metal precursor having a solubility of 0.1 wt %or greater in water.

Metal carbonates that are suitable for use in the practice of thepresent invention include NiCO₃, and the like, metal hydroxycarbonates,such as, for example NiCO₃.2Ni(OH)₂.xH₂O, and the like. Also suitableare metal amine complexes, such as, for example, tetraaminenickelcarbonate (Ni(NH₃)₄(CO₃), tetraaminecobalt carbonate (Co(NH₃)₄CO₃), andthe like. Suitable metal oxides include, for example, NiO, WO₃, CoO,CO₃O₄, CO₂O₃, and the like. Metal hydroxides that are suitable for usein the practice of the present invention include, for example, Ni(OH)₂,Co(OH)₂, W(OH)₂, and the like. Exemplary salts of metal acids that aresuitable for use in the processes of the present invention include, forexample, a tungstate (e.g., a hydrogentungstate, a polymeric W₂O₇ ²⁻, aparatungstate A ([W₇O₂₄]⁶⁻), a paratungstate B ([H₂W₁₂O₄₂]¹⁰⁻), ametatungstate (α-[H₂W₁₂O₄₀]⁶⁻, tungstate Y ([W₁₀O₃₂]⁴⁻), tungstate X(β-[H₂W₁₂O₄₀]⁶⁻), and the like, and hydrates thereof). The salt of themetal acid may be first formed by premixing a metal acid or metal oxide(e.g., H₂WO₄, WO₃, and the like) with a base (e.g., NH₃, a diamine(e.g., ethylene diamine, KOH, NaOH, and the like) to form thecorresponding metal salt in an aqueous solution that can be introducedinto the ensuing metal-carbon mixture. Exemplary metal salts that can beformed in such manner include, for example, (NH₃)₂WO₄, K₂WO₄,(C₂H₈N₂)₂WO₄, and the like. Heterpoly acids that are suitable for use inthe practice of the present invention include tungstosilicic acidhydrate (H₄[Si(W₃O₁₀)₄]xH₂O), phosphotungstic acid hydrate(H₃[P(W₃O₁₀)₄]xH₂O), silicomolybdic acid (H₄SiO₄.12MoO₃). Exemplarymetal carboxylates that are suitable for use as a metal precursor in thepresent invention include metal formates, metal acetates, metalcitrates, metal succinates, metal oxalates, metal lactates, and thelike. Specific examples include Cobalt (III) 2-ethylhexanoate, Cobalt(II) 2-ethylhexanoate ([CH₃(CH₂)₃CH(C₂H)CO₂]2Co), Nickel(II)2-ethylhexanoate ([CH₃(CH₂)₃CH(C₂H₅)CO₂]2Ni), Nickel(II) acetatetetrahydrate (Ni(OCOCH₃)₂.4H₂O), Nickel (III) oxalate dihydrate(NiC₂O₄.2H₂O), Cobalt (III) oxalate dihydrate (CoC₂O₄.2H₂O), and thelike. Exemplary metal carbides that are suitable for use in the practiceof the present invention include, for example, tungsten carbide (WC),and the like. Metal chlorides that are suitable for use in the practiceof the present invention include nickel chloride (NiCl₂), and the like.The term “metal amine complex-containing compound” refers herein to acompound that has a metal complex containing at least one ammonia (NH₃)ligand complexed with a metal ion, and typically, a counterion, Typicalcounterions include, for example carbonate (including, e.g., abicarbonate), a halide, a hydroxide, a carboxylate, and the like. Incertain embodiments, the metal precursor comprises metal that has amelting temperature greater than the carbonization temperature.

A preferred nickel-based precursor is nickel carbonate and hydratesthereof. Preferred tungsten-based precursors include salts of tungsticacid (i.e., where the tungsten is present in the form of a tungstateanion), such as, for example, ammonium paratungstate, ammoniummetatungstate, and the like, and hydrates thereof, as well as solutionsof tungsten trioxide (WO₃) or tungstic acid (H₂WO₄) in base (e.g.,ammonia (NH₃), an amine hydroxide, and the like.

The quantity of metal precursor utilized in the metal-carbon mixturewill vary depending on the quantity of metal desired in the carbonized,shaped metal-carbon product. Those having ordinary skill in the art willbe able to readily compute the quantity of metal precursor required toachieve the desired target wt % of metal in the carbonized, shapedmetal-carbon product. In some embodiments, the quantity of metalprecursor utilized in the metal-carbon mixture is in the range of fromabout 1 wt % to about 90 wt %, and more typically in the range of fromabout 1 wt % to about 85 wt %, from about 1 wt % to about 80 wt %, fromabout 1 wt % to about 75 wt %, from about 1 wt % to about 70 wt %, fromabout 1 wt % to about 65 wt %, from about 1 wt % to about 60 wt %, fromabout 1 wt % to about 55 wt %, from about 1 wt % to about 50 wt %, fromabout 1 wt % to about 45 wt %, from about 1 wt % to about 40 wt %, fromabout 1 wt % to about 35 wt %, from about 1 wt % to about 30 wt %, fromabout 1 wt % to about 25 wt %, or from about 1 wt % to about 20 wt %. Inother embodiments, the quantity of metal precursor in the metal-carbonmixture is in the range of from about 5 wt % to about 70 wt %, fromabout 10 wt % to about 70 wt %, from about 15 wt % to about 70 wt %,from about 5 wt % to about 60 wt %, from about 10 wt % to about 60 wt %,from about 15 wt % to about 60 wt %, from about 20 wt % to about 60 wt%, or from about 25 wt % to about 60 wt %. Often, the quantity of metalprecursor in the metal-carbon mixture is in the range of from about 1 wt% to about 25 wt %, from about 2 wt % to about 25 wt %, from about 3 wt% to about 25 wt %, from about 4 wt % to about 25 wt %, from about 5 wt% to about 25 wt %, or from about 5 wt % to about 20 wt %. In someembodiments, such as, for example, when the metal is a promoter, thequantity of corresponding metal precursor in the metal-carbon mixture isin the range of from about 0.1 wt % to about 10 wt %, from about 0.1 wt% to about 5 wt %, or from about 0.5 wt % to about 5 wt %.

Water-soluble organic binders that are suitable for use in the practiceof the present invention are water-soluble organic compounds that arecapable of being carbonized at a temperature in the range of from about250° C. to about 1000° C., and which exhibit a solubility of at leastabout 1 wt % in water at a temperature of 50° C. In some embodiments,the water-solubility binder exhibits a solubility of at least about 2 wt% at a temperature of 50° C.

Water-soluble organic binders employed in the practice of the presentinvention are water-soluble organic compounds that typically containonly carbon, oxygen, and hydrogen atoms. In some embodiments, however,the water-soluble organic binder may contain other atom species.Suitable water-soluble organic binders are either a carbohydrate orderivative thereof, or a non-carbohydrate compound. The carbohydrateemployed in the practice of the present invention may be amonosaccharide, a disaccharide, an oligosaccharide, a polysaccharide, orderivative thereof. Monosaccharides that are suitable for use in thepractice of the present invention include, for example, glucose,fructose, galactose, ribose, and the like. Suitable disaccharidesinclude, for example, sucrose, lactose, maltose, trehalose, and thelike. Often, the water-soluble organic binder comprises a sugar (i.e., amonosaccharide and/or a disaccharide), either alone, or together with awater-soluble polymer. Exemplary oligosaccharides that are suitable foruse in the practice of the present invention includefructo-oligosaccharides, galacto-oligosaccharides, mannanoligosaccharides, and the like.

Exemplary polysaccharides include, for example, a cellulose (such as,for example, methylcellulose, ethylcellulose, ethylmethylcellulose,hydroxyethylcellulose, hydroxypropylcellulose,methylhydroxyethylcellulose, ethylhydroxyethylcellulose,hydroxypropylmethylcellulose, carboxymethylcellulose, and the like, aswell as mixtures thereof), alginic acid, pectin, an aldonic acid, andthe like, and mixtures thereof.

Suitable carbohydrate derivatives include, for example, polyols (e.g.,sugar alcohols, such as, for example, sorbitol, glycerol, erythritol,threitol, arabitol, xylitol, ribitol, mannitol, galactitol, fucitol,iditol, inositol, volemitol, isomalt, maltitol, lactitol, maltotritol,maltotetraitol, polyglycitol, and the like); sugar acids (e.g., gluconicacid, glucoronic acid, and the like), amino sugars (e.g., glucosamine,and the like), sialic acid, and the like.

Water-soluble non-carbohydrate compounds that are suitable for use inthe practice of the present invention include, for example, awater-soluble non-carbohydrate polymer, a water-soluble fatty acid orsalt thereof, a water-soluble fatty alcohol or ester thereof, and thelike. Water-soluble non-carbohydrate polymers that may be employed as abinder in the present invention include homopolymers, copolymers (orother multi-monomer species-based polymer, e.g., polypeptides,polynucleotides, collagen, gelatin, and the like), hydrogel-formingpolymers, and the like. Suitable non-carbohydrate polymers include, forexample, polyacrylic acids, polyvinylalcohols, polyvinylpyrrolidones,polyvinyl acetate, polyacrylates, polyethers (such as, for example, apolyethylene glycol, and the like), polyols (e.g., glycerol, and thelike), polyethylene oxides, poly-oxo-methlene, polyvinylphthalate, Gumarabic, phenolic resin solutions, polyacrylamides, polylactic acids, andthe like, as well as mixtures and copolymers thereof. Suitableco-polymers include, for example, polylactic-co-glycolic acid, and thelike.

In some embodiments, the water-soluble organic binder comprises awater-soluble polymer having a relatively low number average molecularweight and/or is capable of yielding relatively low viscosity solutions.Accordingly, in various embodiments, the binder comprises a watersoluble polymer, wherein a 2 wt % aqueous solution or a 5 wt % aqueoussolution of the water-soluble polymer has a viscosity of no greater thanabout 500 mPa-s, or no greater than about 400 mPa-s, or no greater thanabout 300 mPa-s, or no greater than about 200 mPa-s, or no greater thanabout 100 mPa-s, or no greater than about 75 mPa-s, or no greater thanabout 50 mPa-s at 25° C. and/or the water soluble polymer has a numberaverage molecular weight (Mn) that is no greater than about 50,000g/mole, or no greater than about 40,000 g/mol, or no greater than about30,000 g/mol, or no greater than about 25,000 g/mol, or no greater thanabout 20,000 g/mol. In some embodiments, the binder comprises awater-soluble polymer, wherein a 2 st % aqueous solution or a 5 wt %aqueous solution of the water-soluble polymer has a viscosity that is inthe range of from about 2 to about 500 mPa-s, from about 2 to about 400mPa-s, from about 2 to about 100 mPa-s, from about 2 to about 75 mPa-s,or from about 2 to about 50 mPa-s at 25° C. In these and otherembodiments, the water-soluble polymer can have a number averagemolecular weight (Mn) that is in the range of from about 2,000 to about50,000 g/mol, from about 5,000 to about 40,000 g/mol, from about 5,000to about 30,000 g/mol, from about 5,000 to about 25,000 g/mol, fromabout 5,000 to about 20,000 g/mol, from about 20,000 to about 50,000g/mol, from about 10,000 to about 40,000 g/mol, from about 10,000 toabout 30,000 g/mol, from about 10,000 to about 25,000 g/mol, or fromabout 10,000 to about 20,000 g/mol. Water-soluble organic binders thatare suitable for use in the practice of the present invention includethose described in published PCT application WO 2015/168327, as well asU.S. applications U.S. Ser. No. 62/247,721 and U.S. Ser. No. 15/131,829,each of which is incorporated herein by reference

The quantity of binder employed in the metal-carbon mixture is typicallyin the range of from about 10 wt % to about 50 wt %. In someembodiments, the quantity of binder is in the range of from about 10 wt% to about 45 wt %, from about 15 wt % to about 40 wt %, from about 20wt % to about 35 wt %, or from about 25 wt % to about 35 wt %.

One of ordinary skill will appreciate that the binder may be a mixtureof the above-described compounds. For example, in certain embodiments,the binder comprises at least one monosaccharide or disaccharide, and atleast one polysaccharide. In these embodiments, the weight ratio ofmono- or di-saccharide to polysaccharide is typically in the range offrom about 2:1 to about 30:1. More typically, the weight ratio is fromabout 3:1 to about 25:1, from 3:1 to about 20:1, from about 5:1 to about20:1, or from about 10:1 to about 20:1. In a preferred embodiment, thebinder comprises a mixture of glucose and a cellulose, such as, forexample, hydroxyethylcellulose.

As used herein, the term “carbonaceous material” refers to elementalcarbon in the form of graphite or an amorphous form of carbon. When thecarbonaceous material employed in the practice of the present inventionis an amorphous carbon, it is typically a carbon black or an activatedcarbon. The choice of carbonaceous material will depend on the desiredproperties for the metal-containing carbon composite material. It hasbeen discovered that the porous nature of the underlying carbonaceousmaterial corresponds substantially to the corresponding properties inthe (carbonized) metal-containing carbon composite material.

Accordingly, when a relatively low porosity, low specific surface areacomposite material is desired, carbon black is typically employed. Whena relatively high porosity, high specific surface area compositematerial is desired, activated carbon is typically utilized. In someembodiments, it may be desired to use carbon nanotubes as thecarbonaceous material. In certain applications, e.g., when a highlyelectrically-conductive material is desired, it may be desired to usegraphite as the carbonaceous material. The foregoing carbonaceousmaterials are readily available from commercial suppliers. Specificcarbon blacks that are suitable for use in the processes of the presentinvention include those described in published PCT application WO2015/168327, as well as U.S. applications U.S. Ser. No. 62/247,721 andU.S. Ser. No. 15/131,829, each of which is incorporated herein byreference.

The weight ratio of binder to carbonaceous material in the metal-carbonmixture is typically at least about 1:4, at least about 1:3, at leastabout 1:2, at least about 1:1, or at least 1.5:1. The weight ratio ofbinder to carbonaceous material in the metal-carbon mixture can also befrom about 1:4 to about 3:1, from about 1:4 to about 1:1, from about 1:3to about 2:1, from about 1:3 to about 1:1, or about 1:1. Typically, thequantity of carbonaceous material in the metal-carbon mixture is atleast about 35 wt % or more such as at least about 40 wt %, at leastabout 45 wt %, as at least about 50 wt %, as at least about 55 w.%, atleast about 60 wt %, at least about 65 wt %, or at least about 70 wt %on a dry weight basis. In various embodiments, the quantity ofcarbonaceous material in the metal-carbon mixture is from about 35 wt. %to about 80 wt %, from about 35 wt % to about 75 wt %, from about 40 wt% to about 80 wt %, or from about 40 wt % to about 75 wt % on a dryweight basis.

The metal-carbon mixture typically comprises a quantity of carbonaceousmaterial in the range of from about 10 wt % to about 80 wt %, and moretypically in the range of from about 15 wt % to about 75 wt %, fromabout 15 wt % to about 70 wt %, from about 15 wt % to about 65 wt %,from about 15 wt % to about 60 wt %, from about 15 wt % to about 55 wt%, from about 15 wt % to about 50 wt %, from about 15 wt % to about 45wt %, from about 15 wt % to about 40 wt %, from about 15 wt % to about35 wt %, from about 20 wt % to about 70 wt %, from about 20 wt % toabout 65 wt %, from about 20 wt % to about 60 wt %, from about 20 wt %to about 55 wt %, from about 20 wt % to about 50 wt %, from about 20 wt% to about 45 wt %, from about 20 wt % to about 40 wt %, from about 20wt % to about 35 wt %, or from about 25 wt % to about 35 Wt %.

When a carbon black is used, it may be a non-conductive or a conductivecarbon black. The carbon black materials used to prepare the shapedporous metal-carbon products of the present invention also generallyhave specific pore volumes greater than about 0.1 cm³/g, greater thanabout 0.2 cm³/g, or greater than about 0.3 cm³/g. The specific porevolume of the carbon black materials may be in the range from about 0.1cm³/g to about 1 cm³/g, from about 0.1 cm³/g to about 0.9 cm³/g, fromabout 0.1 cm³/g to about 0.8 cm³/g, from about 0.1 cm³/g to about 0.7cm³/g, from about 0.1 cm³/g to about 0.6 cm³/g, from about 0.1 cm³/g toabout 0.5 cm³/g, from about 0.2 cm³/g to about 1 cm³/g, from about 0.2cm³/g to about 0.9 cm³/g, from about 0.2 cm³/g to about 0.8 cm³/g, fromabout 0.2 cm³/g to about 0.7 cm³/g, from about 0.2 cm³/g to about 0.6cm³/g, from about 0.2 cm³/g to about 0.5 cm³/g, from about 0.3 cm³/g toabout 1 cm³/g, from about 0.3 cm³/g to about 0.9 cm³/g, from about 0.3cm³/g to about 0.8 cm³/g, from about 0.3 cm³/g to about 0.7 cm³/g, fromabout 0.3 cm³/g to about 0.6 cm³/g, or from about 0.3 cm³/g to about 0.5cm³/g. Carbon black materials with these specific pore volumes provide avolume sufficient to provide uniform wetting and good dispersion of thecatalytically active components while enabling sufficient contactbetween the reactant molecules and the catalytically active surface.Mean pore diameters and pore volumes are determined in accordance withthe procedures described in E. P. Barrett, L. G. Joyner, P. P. Halenda,J. Am. Chem. Soc. 1951, 73, 373-380 (referred to herein as the “BJHmethod”), and ASTM D4222-03(2008) Standard Test Method for Determinationof Nitrogen Adsorption and Desorption Isotherms of Catalysts andCatalyst Carriers by Static Volumetric Measurements, which areincorporated herein by reference.

Typically, the carbon black has a BET specific surface area in the rangeof from about 20 m²/g to about 500 m²/g. In some embodiments, the BETspecific surface area is in the range of from about 20 m²/g to about 350m²/g, from about 20 m²/g to about 250 m²/g, from about 20 m²/g to about225 m²/g, from about 20 m²/g to about 200 m²/g from about 20 m²/g toabout 175 m²/g, from about 20 m²/g to about 150 m²/g, from about 20 m²/gto about 125 m²/g, or from about 20 m²/g to about 100 m²/g, from about25 m²/g to about 500 m²/g, from about 25 m²/g to about 350 m²/g, fromabout 25 m²/g to about 250 m²/g, from about 25 m²/g to about 225 m²/g toabout 150 m²/g, from about 25 m²/g to about 125 m²/g, from about 25 m²/gto about 100 m²/g, from about 30 m²/g to about 500 m²/g, from about 30m²/g to about 350 m²/g from about 30 m²/g to about 250 m²/g, from about30 m²/g to about 225 m²/g, from about 30 m²/g to about 200 m²/g, fromabout 30 m²/g to about 175 m²/g, from about 30 m²/g to about 150 m²/g,from about 30 m²/g to about 125 m²/g, or from about 30 m²/g to about 100m²/g. As used herein, the term “BET specific surface area” refers tospecific surface area as determined from nitrogen adsorption data inaccordance with the method of Brunauer, Emmet and Teller, as describedin J. Am. Chem. Soc. (1938) 60:309-331 and ASTM Test Methods D3663,D6556 or D4567 (Standard Test Methods for Surface Area Measurements byNitrogen Adsorption), which are incorporated herein by reference.

In some embodiments, e.g., where a high surface area, metal-carbonproduct is desired, the carbonaceous material is an activated carbon.Activated carbons that are suitable for use in the practice of thepresent invention typically exhibit a BET specific surface area that isgreater than 500 m²/g. In some embodiments, the BET specific area of theactivated carbon is in the range of from about 550 m²/g to about 3500m²/g. In certain embodiments, the BET specific surface area of theactivated carbon is in the range of from about 600 m²/g to about 2500m²/g, from about 600 m²/g to about 2250 m²/g, from about 600 m²/g toabout 2000 m²/g, or from about 700 m²/g to about 2000 m²/g. In otherembodiments, the BET specific surface of the activated carbon is in therange of from about 800 m²/g to about 2500 m²/g, from about 800 m²/g toabout 2000 m²/g, or from about 1000 m²/g to about 2000 m²/g.

In other embodiments, the carbonaceous material is a graphite. Thegraphite may be in either natural or synthetic form of fine grain,medium grain, or coarse grain grades. Typically, the graphite issynthetic graphite. Graphites that are suitable for use in connectionwith the present invention, are in powder form and have a bulk densitythat is greater than 1 g/cm³, and more typically, the bulk density isgreater than about 1.1 g/cm³, and in some embodiments, greater thanabout 1.2 g/cm³. Graphites employed in the practice of the presentinvention are typically porous, having a porosity in the range of fromabout 0.5 vol % to about 60 vol %, and more often in the range of fromabout 0.5 vol % to about 55 vol %.

In certain embodiments, the carbonaceous material is a mixture of anytwo or more forms of carbon selected from the group consisting of acarbon black, an activated carbon, and a graphite. Use of such mixturesallows one to achieve properties that are intermediate with respect tothe properties associated with each individual form of carbon. Forexample, though graphite typically has a BET surface area of less than20 m²/g, use of a blend of graphite with carbon black or activatedcarbon in the appropriate relative quantities can result in a mixturehaving a BET surface area greater than 20 m²/g.

The amount of water utilized in the metal-carbon mixture is typically inthe range of from about 15 wt % to about 70 wt %. More typically, it isin the range of from about 15 wt % to about 65 wt %, from about 15 wt %to about 60 wt %, from about 15 wt % to about 55 wt %, from about 15 wt% to about 50 wt %, from about 15 wt % to about 45 wt %, from about 20wt % to about 40 wt %, or from about 25 wt % to about 40 wt %.

In certain embodiments, the metal-carbon mixture comprises: from about0.1 wt % to about 50 wt % metal precursor; from about 20 wt % to about35 wt % carbonaceous material; from about 20 wt % to about 35 wt %monosaccharide or disaccharide; from about 0.5 wt % to about 5 wt %polysaccharide; and from about 25 wt % to about 45 wt % water.

The metal-carbon mixture may contain additives such as, for exampleforming aids (e.g., lubricants, such as, for example, waxes (e.g.,stearic acid and salts thereof), and the like); wetting agents (e.g.,surfactants); porogens; peptization agents; an organic solvent; and thelike, as well as combinations of two or more thereof.

During the mixing step, the order of addition of the components is notcritical. However, to facilitate ease of mixing, it may be desirable topremix certain components together prior to mixing all of the componentstogether. For example, when the metal precursor is water-soluble, it maybe pre-mixed with water and optionally, the water-soluble organicbinder, prior to adding the carbonaceous material to the mixture.Typically, the water and water-soluble organic binder are premixedtogether to form a binder solution. In embodiments where the metalprecursor is water-insoluble, it may be desirable to premix the metalprecursor with the carbonaceous material, followed by mixing theresulting combined dry mix with binder solution.

The metal-carbon mixture may be heated to facilitate dissolution ofsoluble components during mixing, such as, for example, anywater-soluble polymers. For example, in some embodiments, themetal-carbon mixture, or re-mixture of water and binder and optionally awater-soluble metal precursor are heated during the mixing step to atemperature of at least about 50° C., at least about 60° C., or at leastabout 70° C. In various embodiments, the water and binder can be heatedto a temperature of from about 50° C. to about 95° C., from about 50° C.to about 90° C., or from about 60° C. to about 85° C. Mixing can becarried out using industrial mixers such as, for example, a mix muller,a planetary mixer, a drum mixer, a pan mixer, a twin shaft mixer, acement mixer, or other type of mixer suitable for mixing high viscositymaterials.

After the mixing step, the metal-carbon mixture is pliable and can bereadily manipulated into a desired shape or form during a shaping stepto form a green, shaped metal-carbon product. As used herein, the term“green shaped metal-carbon product” refers to the metal-carbon mixtureor partially or fully dehydrated mixture thereof, formed into a desiredshape, but not yet carbonized. During the shaping step, the metal-carbonmixture is converted into a desired shape using a method such as, forexample, pressing, casting, injection molding, extruding, spreading as apaste, pelletizing, granulating, calendering, 3-D printing, and thelike, and optionally subsequently breaking such shapes into smallerpieces (i.e., smaller shaped pieces). The shaping step may be carriedout at an elevated temperature to reduce the viscosity of the mixtureand corresponding forces required to manipulate the material into thedesired shape. In some embodiments, the shaping step is carried out at atemperature of at least about 50° C., at least about 60° C., or at leastabout 70° C. In various embodiments, the shaping step is carried out ata temperature of from about 50° C. to about 95° C., from about 50° C. toabout 90° C., or from about 60° C. to about 85° C. Suitable methods forshaping the metal-carbon mixture include those described in publishedPCT application WO 2015/168327, as well as U.S. applications U.S. Ser.No. 62/247,721 and U.S. Ser. No. 15/131,829 for forming or shaping acarbon black mixture, each of which is incorporated herein by reference.

In some embodiments, it may be desirable to remove all or a portion ofthe water from the green, shaped metal-carbon product in a drying step,prior to carrying out the carbonization step. Typically, the drying stepis carried out either under ambient temperature (e.g., about 20° C.) andpressure, or at a temperature in the range of from about 20° C. to about175° C., from about 20° C. to about 150° C., from about 40° C. to about120° C., from about 60° C. to about 120° C., from about 90° C. to about175° C., from about 90° C. to about 150° C., from about 100° C. to about150° C., or from about 100° C. to about 140° C. The drying step may becarried out under a vacuum or otherwise reduced pressure, relative toambient pressure. Methods for drying the green, shaped carbon productthat are suitable for use in the processes of the present inventioninclude those described in published PCT application WO 2015/168327, aswell as U.S. applications U.S. Ser. No. 62/247,721 and U.S. Ser. No.15/131,829 for drying a shaped carbon composite, each of which isincorporated herein by reference.

The carbonization step is typically conducted by heating the green,shaped metal-carbon product to a temperature in the range of from about250° C. to about 1,000° C., from about 300° C. to about 900° C., fromabout 300° C. to about 850° C., from about 300° C. to about 800° C.,from about 350° C. to about 850° C., from about 350° C. to about 800°C., from about 350° C. to about 700° C., from about 400° C. to about850° C. or from about 400° C. to about 800° C. Suitable methods forcarbonizing the green, shaped metal-carbon product include thosedescribed in. published PCT application WO 2015/168327, as well as U.S.applications U.S. Ser. No. 62/247,721 and U.S. Ser. No. 15/131,829 forcarbonizing shaped carbon composites, each of which is incorporatedherein by reference. The carbonization step, inter alia, renders thewater-soluble organic binder, water-insoluble.

The processes described herein advantageously allow for theincorporation of a wide variety of metal species into a porous, yetdurable carbon-based material. Exemplary porous shaped metal-carbonproducts include, for example, porous, shaped Ni-carbon products; porousshaped W-carbon products; porous shaped Co-carbon products; and thelike, as well as such products having a further metal deposited thereon(on internal and external surfaces). As used herein, when a specificmetal is recited as the “metal” or “metal component” with reference tothe metal-carbon product, what is being referred to is the metalcorresponding to the metal precursor compound, where such metal resideson and/or in the porous shaped metal-carbon product after thecarbonization step. Without wishing to be bound by any theory, it isbelieved that in situ carbonization of the metal precursor within themetal-carbon mixture may impact the distribution of metal in/on theporous, shaped metal-carbon product, as compared to the distribution ofmetal in/on a corresponding control product. The “corresponding controlproduct” in this case being prepared from a green, shaped carbon productthat does not have metal incorporated in it, but has metal added to itpost-carbonization (e.g., by impregnation) The difference may bepotentially more pronounced with the use of a water-insoluble metalprecursor in the processes of the present invention.

Without wishing to be bound by theory, it is believed that carbonizationof the metal-carbon mixture may also alter the textural properties(e.g., surface area and porosity) of the carbonized product, as comparedto product from carbonization of the green product without the metalincorporated. When a porous, shaped tungsten (W)-carbon product wasprepared, the BET surface area was observed to be higher than acorresponding shaped carbon product prepared without the tungsten.Likewise, the BJH specific pore volume was lower in the W-carbon productof the present invention, as compared to without it. Furthermore, theaverage pore diameter was relatively larger in the W-carbon product ofthe present invention as compared to a corresponding shaped carbonproduct prepared without the tungsten.

The processes of the present invention provide further advantages. Forexample, when the metal precursor is capable of being decomposed andreduced to a metal at the carbonization temperature (i.e., in situreduction), a further reduction step may be avoided. Such a process isattractive economically. In various embodiments, however, it may bedesired to reduce the metal in the shaped metal-carbon product bycontacting the product with a reducing agent, such as, for example,hydrogen (e.g., by flowing 5% H₂ in N₂ at 350 C for 3 hours). Reductionof the shaped metal-carbon product is illustrated in the Examples.

The metal component of the porous, shaped metal-carbon product istypically present at a metal loading in the range of from about 0.1 wt %to about 50 wt %, from about 0.1 wt % to about 45 wt %, from 0.1 wt % toabout 40 wt %, from about 0.1 wt % to about 35 wt %, from about 0.1 wt %to about 30 wt %, or from about 0.1 wt % to about 25 wt % of the totalweight of the porous shaped metal-carbon product. In some embodiments,the metal loading is in the range of from about 0.5 wt % to about 50 wt%, from about 1 wt % to about 50 wt %, from about 1 wt % to about 45 wt%, from about 1 wt % to about 40 wt %, from about 1 wt % to about 35 wt%, from about 1 wt % to about 30 wt %, from about 1 wt % to about 25 wt%, or from about 1 wt % to about 20 wt % of the total weight of theporous shaped metal-carbon product.

The carbonized, shaped metal-carbon product typically has a carboncontent in the range of from about 50 wt % to about 99.9 wt %. Moretypically, the carbon content is in the range of from about 55 wt % toabout 99 wt %, from about 60 wt % to about 99 wt %, from about 65 wt %to about 99 wt %, from about 70 wt % to about 99 wt %, or from about 75wt % to about 99 wt % of the total weight of the porous shapedmetal-carbon product. Carbon content of the shaped metal-carbon productis determined by the following formula: [(Weight of carbonaceousmaterial used to prepare the metal-carbon mixture)/(Weight of the porousshaped metal-carbon product)]×100%.

When carbon black is utilized during preparation of the carbonizedshaped metal-carbon product, the product is typically a mesopore-denseproduct having a high concentration of mesopores with diameters in therange of from about 10 nm to about 100 nm or from about 10 nm to about50 nm. In some embodiments, at least about 50%, at least about 60%, atleast about 70%, at least about 80%, or at least about 90% of the porevolume of these shaped metal-carbon products is attributable to poreshaving a pore diameter of from about 10 nm to about 100 nm as measuredby the BJH method (on the basis of pores having a diameter of from 1.7nm to 100 nm). The term “mesopore-dense metal-containing carbon-basedmaterials” refers herein to metal-containing carbon-based materialsprepared in accordance with the processes described herein where carbonblack is employed as the carbonaceous material.

In certain mesopore-dense, carbonized, shaped metal-carbon products ofthe present invention, the contribution to pore volume of pores having apore diameter in the range of from about 10 nm to about 100 nm (on thebasis of pores having a diameter of from 1.7 nm to 100 nm) is from about50% to about 95%, from about 50% to about 90%, from about 50% to about80%, from about 60% to about 95%, from about 60% to about 90%, fromabout 60% to about 80%, from about 70% to about 95%, from about 70% toabout 90%, from about 70% to about 80%, from about 80% to about 95%, orfrom about 80% to about 90% of the pore volume as measured by the BJHmethod (on the basis of pores having a diameter of from 1.7 nm to 100nm). In other embodiments, the contribution to pore volume of poreshaving a pore diameter in the range of from about 10 nm to about 50 nm(on the basis of pores having a diameter of from 1.7 nm to 100 nm) is atleast about 35%, at least about 40%, at least about 45%, or at leastabout 50% of the pore volume as measured by the BJH method (on the basisof pores having a diameter of from 1.7 nm to 100 nm).

Typically, these mesopore-dense, carbonized, shaped metal-carbonproducts possess a relatively low concentration of pores having a porediameter less than 10 nm, less than 5 nm, or less than 3 nm. In certainembodiments, no more than about 10%, no more than about 5%, or no morethan about 1% of the pore volume of these materials is less than 10 nm,less than 5 nm, or less than 3 nm, as measured by the BJH method (on thebasis of pores having a diameter from 1.7 nm to 100 nm). In otherembodiments, the contribution to pore volume of pores having a porediameter that is less than 10 nm, less than 5, or less than 3 nm, is inthe range of from about 0.1% to about 10%, from about 0.1% to about 5%,from about 0.1% to about 1%, from about 1% to about 10%, from about 0.1%to about 5%, from about 0.1% to about 1%, from about 1% to about 10%, orfrom about 1% to about 5%, as measured by the BJH method (on the basisof pores having a diameter from 1.7 nm to 100 nm).

In some embodiments, the mesopore-dense, carbonized, shaped metal-carbonproducts of the present invention have a pore size distribution with noobservable peaks below 10 nm, and in some embodiments, no observablepeaks below 5 nm. In these and other embodiments, the mesopore-dense,carbonized, shaped metal-carbon products have a pore size distributionwith the peak of the distribution at a pore size diameter that isgreater than about 5 nm, greater than about 7.5 nm, greater than about10 nm, greater than about 12.5 nm, greater than about 15 nm, or greaterthan about 20 nm, and usually less than about 100 nm, less than about 90nm, less than about 80 nm, or less than about 70 nm.

Mesopore-dense, carbonized, shaped metal-carbon products of the presentinvention typically have a BET specific surface area in the range offrom about 20 m²/g to about 500 m²/g. In some embodiments, the BETspecific surface area is in the range of from about 20 m²/g to about 350m²/g, from about 20 m²/g to about 250 m²/g, from about 20 m²/g to about225 m²/g, from about 20 m²/g to about 200 m²/g from about 20 m²/g toabout 175 m²/g, from about 20 m²/g to about 150 m²/g, from about 20 m²/gto about 125 m²/g, or from about 20 m²/g to about 100 m²/g, from about25 m²/g to about 500 m²/g, from about 25 m²/g to about 350 m²/g, fromabout 25 m²/g to about 250 m²/g, from about 25 m²/g to about 225 m²/g toabout 150 m²/g, from about 25 m²/g to about 125 m²/g, from about 25 m²/gto about 100 m²/g, from about 30 m²/g to about 500 m²/g, from about 30m²/g to about 350 m²/g from about 30 m²/g to about 250 m²/g, from about30 m²/g to about 225 m²/g, from about 30 m²/g to about 200 m²/g, fromabout 30 m²/g to about 175 m²/g, from about 30 m²/g to about 150 m²/g,from about 30 m²/g to about 125 m²/g, or from about 30 m²/g to about 100m²/g.

The specific pore volume of mesopore-dense, carbonized, shapedmetal-carbon products prepared according to the processes describedherein, are typically greater than about 0.1 cm³/g, as measured by theBJH method (on the basis of pores having a diameter in the range of from1.7 nm to 100 nm). More typically the specific pore volume of themesopore-dense, shaped metal-carbon products is greater than about 0.2cm³/g or greater than 0.3 cm³/g, as measured by the BJH method (on thebasis of pores having a diameter in the range of from 1.7 nm to 100 nm).In some embodiments, the mesopore-dense, carbonized, shaped metal-carbonproduct of the present invention have a specific pore volume of poreshaving a diameter in the range of from 1.7 nm to 100 nm, as measured bythe BJH method, that is from about 0.1 cm³/g to about 1.5 cm³/g, fromabout 0.1 cm³/g to about 0.9 cm³/g, from about 0.1 cm³/g to about 0.8cm³/g, from about 0.1 cm³/g to about 0.7 cm³/g, from about 0.1 cm³/g toabout 0.6 cm³/g, from about 0.1 cm³/g to about 0.5 cm³/g from about 0.2cm³/g to about 0.8 cm³/g, from about 0.2 cm³/g to about 0.7 cm³/g, fromabout 0.2 cm³/g to about 0.6 cm³/g, from about 0.2 cm³/g to about 0.5cm³/g, from about 0.3 cm³/g to about 1 cm³/g, from about 0.3 cm³/g toabout 0.9 cm³/g, from about 0.3 cm³/g to about 0.8 cm³/g to about 1cm³/g, from about 0.3 cm³/g to about 0.9 cm³/g, from about 0.3 cm³/g toabout 0.8 cm³/g, from about 0.3 cm³/g to about 0.7 cm³/g, from about 0.3cm³/g to about 0.6 cm³/g, or from about 0.3 cm³/g to about 0.5 cm³/g.

Mesopore-dense, carbonized, shaped metal-carbon products of the presentinvention typically exhibit relatively high mechanical strength, andstability, particularly under aqueous conditions. In some embodiments,these materials comprise a radial piece crush strength of greater thanabout 4.4 N/mm (1 lb/mm). In other embodiments the mesopore-dense,carbonized, shaped metal-carbon products comprise a radial piece crushstrength of greater than about 8.8 N/mm (2 lbs/mm), or greater thanabout 13.3 N/mm (3 lbs/mm). In certain embodiments, the radial piececrush strength of the mesopore-dense, carbonized, shaped metal-carbonproduct of the present invention is in the range of from about 4.4 N/mm(1 lb/mm) to about 88 N/mm (20 lbs/mm), from about 4.4 N/mm (1 lb/mm) toabout 66 N/mm (15 lbs/mm), or from about 8.8 N/mm (1 lb/mm) to about 44N/mm (10 lbs/mm). As used herein, the term “radial piece crush strength”refers to the piece crush strength test protocols described in ASTMD4179 or ASTM D6175, which are incorporated herein by reference. Thoughsome of the test methods limit the particles to a defined dimensionalrange, geometry, or method of manufacture, crush strength of irregularlyshaped particles and particles of varying dimension and manufacture maynevertheless be adequately measured by these and similar test methods.

In some embodiments, mesopore-dense, carbonized, shaped metal-carbonproducts prepared in accordance with the processes described hereinexhibit attrition resistance and abrasion resistance characteristics. Inthese embodiments, the mesopore-dense, carbonized, shaped metal-carbonproducts (which for the purposes of this determination, is prepared inthe form of an extrudate) typically exhibit a rotating drum attritionindex, as measured in accordance with ASTM D4058-96, of greater than atleast about 85 wt % retained on a 20-mesh sieve after a period ofcontinuous rotation in the rotating test cylinder at 55 RPMs for 35minutes. In certain embodiments, these materials exhibit a rotating drumattrition index of greater than at least about 90 wt %, greater thanabout 91 wt %, greater than about 92 wt %, greater than about 93 wt %,greater than about 94 wt %, greater than about 95 wt %, greater thanabout 96 wt %, greater than about 97 wt %, greater than about 98 wt %,or greater than about 99 wt % retained on a 20-mesh sieve in theabove-described attrition test method.

Mesopore-dense, carbonized, shaped metal-carbon products of the presentinvention typically exhibit minimal abrasion loss after a duration ofintense horizontal agitation. As used herein, the term “abrasion loss”refers to a measurement of the resistance of a material to attritionwear due to intense horizontal agitation of particles within theconfines of a 30-mesh sieve. The material is tested as follows: (1) thematerial to be tested is first de-dusted on a 20-mesh sieve by gentlymoving the sieve side-to-side at least 20 times; (2) the de-dustedsample is weighed and then transferred to the inside of a clean, 30-meshsieve stacked above a clean sieve pan for the collection of fines; (3)the completed sieve stack is then assembled onto a sieve shaker (e.g.,RO-Tap RX-29 sieve shaker from W.S. Tyler Industrial Group, Mentor, OH),covered securely and shaken for about 30 minutes; (4) the collectedfines generated are weighed; and (5) percent abrasion loss by weight iscalculated by dividing the weight of collected fines by the de-dustedsample weight. In some embodiments, the mesopore-dense, carbonized,shaped metal-carbon products of the present invention exhibits ahorizontal agitation sieve abrasion loss of less than about 5%, lessthan about 3%, less than about 2%, less than about 1%, less than about0.5%, less than about 0.2%, less than about 0.1%, less than about 0.05%,or less than about 0.03%.

In certain applications, a relatively high surface area, shapedmetal-carbon product may be desired, i.e., having a BET specific surfacearea of greater than about 500 m²/g. The term “high surface area, shapedmetal-carbon product” is used herein to refer to a shaped metal-carbonproduct prepared according to the methods of the present invention wherethe carbonaceous material is an activated carbon. High surface area,shaped metal-carbon products of the present invention typically exhibita BET specific surface area that is greater than 500 m²/g. In someembodiments, the BET specific area of these materials is in the range offrom about 550 m²/g to about 3500 m²/g. In certain embodiments, the BETspecific surface area of these high surface materials is in the range offrom about 600 m²/g to about 2500 m²/g, from about 600 m²/g to about2250 m²/g, from about 600 m²/g to about 2000 m²/g, or from about 700m²/g to about 2000 m²/g. In other embodiments, the BET specific surfaceare of the high surface area, carbonized, shaped metal-carbon productsis in the range of from about 800 m²/g to about 2500 m²/g, from about800 m²/g to about 2000 m²/g, or from about 1000 m²/g to about 2000 m²/g.

High surface area, shaped metal-carbon products of the present inventiontypically possess higher concentrations of pores having a pore diameterless than 10 nm than the mesopore-dense, carbonized, shaped metal-carbonproducts described herein. Typically, the contribution to pore volume ofpores having a pore diameter that is less than 10 nm, is greater than10%, greater than about 20%, or greater than about 25%, as measured bythe BJH method (on the basis of pores having a diameter from 1.7 nm to100 nm).

In some embodiments, it may be desirable to employ graphite as thecarbonaceous material in the preparation of the products of the presentinvention when, for example, improved electrical conductivity isdesired. When graphite alone is employed as the carbonaceous material,the shaped metal-carbon products typically have a BET specific surfacearea of less than 20 m²/g. However, as described above, mixtures ofgraphite with carbon black and/or activated carbon can be utilized inthe metal-carbon mixture to tailor the porosity for the desiredapplication.

The porous shaped metal-carbon products of the present invention may bethermally or chemically treated to modify its physical and/or chemicalcharacteristics. For example, the products may be chemically treatedwith an oxidant to produce a more hydrophilic surface. In someembodiments, the porous shaped metal-carbon product may besurface-treated using known methods, to attach a desired functionalgroup onto the surfaces of the material. See, e.g., WO 2002/018929, WO97/47691, WO99/23174, and WO99/31175, which are incorporated herein byreference.

In certain embodiments, it may be desired to deposit additional metalonto the surfaces of the porous, shaped metal-carbon products of thepresent invention (including both internal pore surfaces, and exteriorsurfaces of the material), such as for use in certain catalyticapplications. In these embodiments, a second metal (or precursorthereof) is deposited onto the surfaces of the porous shapedmetal-carbon products of the present invention, where the second metalcomprises a metal that is the same as or different from the metal in thefirst metal precursor (i.e., the metal precursor incorporated into themetal-carbon mixture).

For catalytic applications, the second metal and metal precursor can beany metal/metal precursor known to be useful in catalyticapplications/catalyst manufacture. The second metal or precursor thereofcan comprise a base metal or a noble metal. In some embodiments, thesecond metal or precursor thereof comprises a metal selected from groupsIV, V, VI, VII, VIII, IX, X, XI, XII, and XIII. In various embodiments,the metal is a d-block metal. Exemplary d-block metals include, forexample, Ni, Co, W, Cu, Zn, Fe, Mo, Ni, Rh, Pd, Ag, Os, Ir, Pt, Au, andthe like.

In other embodiments, the second metal or precursor thereof comprises ametal selected from the group consisting of Cu, Pb, Ni, Zn, Fe, Mo, Al,Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb,Rh, T, Ru, Rh, Pd, Ag, Os, Ir, Pt, or Au. Often, the second metal is anoble metal. In specific embodiments, the second metal or precursorthereof comprises a metal selected from the group consisting of Cu, Pb,Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge,V, Ga, Hf, In, Nb, Rh, and Tl.

In this step, the shaped metal-carbon product is typically contactedwith a solubilized metal precursor in a liquid medium using a knownmethod, such as, for example, incipient wetness, ion-exchange,deposition-precipitation, coating, vacuum impregnation, and the like. Insome embodiments, following deposition of the second metal, theresulting material is optionally dried, for example at a temperature ofat least about 50° C., more typically, at least about 120° C. for aperiod of time, that is typically at least about one hour, moretypically, at least about three hours or more. Alternatively, the dryingmay be conducted in a continuous or staged manner where independentlycontrolled temperature zones (e.g., 60° C., 80° C., and 120° C.) areutilized. Typically, drying is initiated by raising the temperature ofthe wet material to a temperature initially below the boiling point ofthe liquid medium, then increasing the temperature.

Following deposition and optional drying, the resulting product isheated in the presence of a reducing agent, such as, for example,hydrogen (e.g., a forming gas of 5% H₂ and 95% N₂), to reduce the metalprecursor to the metal. The temperature at which the heating isconducted is typically in the range of from about 150° C. to about 600°C., from about 200° C. to about 500° C., or from about 100° C. to about400° C. Heating is typically conducted for a period of time in the rangeof from about 1 hour to about 5 hours or from about 2 hours to about 4hours. Reduction may also be carried out in the liquid phase. Forexample, metal deposition on the porous shaped metal-carbon product canbe carried out in a fixed bed with liquid containing a reducing agentpumped through the static composite material. In some embodiments, theresulting catalyst material is calcined, for example, at a temperatureof at least about 200° C. for a period of time (e.g., at least aboutone, two, or three hours). The deposition of a second metal onto thesurfaces of the shaped metal-carbon product, followed by drying,reduction, and depleted air calcination is illustrated in Example 7.

In some embodiments, the surface-deposited metal(s) are present in therange of from about 0.1% to about 50%, from about 0.1% to about 25%,from about 0.1% to about 10%, from about 0.1% to about 5%, from about0.25% to about 50%, from about 0.25% to about 25%, from about 0.25% toabout 10%, from about 0.25% to about 5%, from about 1% to about 50%,from about 1% to about 25%, from about 1% to about 10%, from about 1% toabout 5%, from about 5% to about 50% from about 5% to about 25% or fromabout 5% to about 10%,by weight of the porous, carbonized, shapedmetal-carbon product. When the surface-deposited metal is a noble metal,it is typically present in a quantity in the range of from about 0.25 wt% to about 10 wt %. When the surface-deposited metal is a non-noblemetal, it is often present in a quantity in the range of from about 0.1%to about 50 wt %.

The porous, shaped metal-carbon products of the present invention areparticularly useful as catalysts. The type of catalytic activity can becustomized for a particular reaction by changing the type of metal usedin the metal precursor as demonstrated in the Examples. In someembodiments, the catalytic activity is a hydrogenation activity, adeoxyhydrogenation activity, an oxidation activity, a reductionactivity, a dehydration activity, or other known catalytic activityusing known active metals which can be conducted in either a gaseous orliquid medium. The porous shaped metal-carbon products may be employedas catalysts in batch, semi-batch or continuous reactor formats that areknown in the art, such as, for example, fixed bed reactors, trickle bedreactors, slurry phase reactors, moving bed reactors, and the like. Theproducts are suitable for use in either gaseous or liquid phasereactions. The porous shaped metal-carbon products are compatible with awide range of solvents, including organic solvents, as well as water,and combinations thereof. Suitable compatible solvents include, forexample, alcohols, such as, for example, ethanol, n-propanol,isopropanol, n-butanol, t-butanol, iso-butanol, sec-butanol, and thelike; esters, such as, for example, methyl acetate, ethyl acetate,propyl acetate, butyl acetate, and the like; ethers, such as, forexample, dioxane, glyme, diglyme, triglyme, tetraglyme, and the like;water; and mixtures thereof.

In one embodiment, the present invention provides a process forproducing 2,5-bis-hydroxymethylfuran (BHMF) from 5-hydroxymethylfurfural(IMF), the method comprising:

contacting HMF with hydrogen in the presence of a hydrogenation catalystcomprising a porous, shaped metal-carbon product of the presentinvention to form BHMF, wherein the metal component of the porous,shaped metal-carbon product is selected from the group consisting of Ni,Zn, Co, Cu, Ag, Pt, Pd, Fe, Ru, Au, W, Sb, Bi, Pb, and combinationsthereof. In some embodiments, the metal component of the porous shapedmetal-carbon product is a combination of metals selected from the groupconsisting of Co/Cu, Ni/Cu, Ag/Ni, Ag/Co and Ag/Ru. Typically, the metalcomponent of the porous shaped metal-carbon product of the presentinvention is a metal selected from the group consisting of Ni, Cu, andmixtures thereof.

The porous, shaped metal-carbon product typically comprises the metalcomponent at a loading in the range of from about 0.5 wt % to about 99wt %. In some embodiments, the loading is in the range of from about 0.1wt % to about 25 wt %, or in the range of from about 0.1 wt % to about20 wt %, or in the range of from about 0.1 wt % to about 18 wt %. Whenthe porous, shaped metal-carbon producte comprises two different speciesof metal components, M1 and M2, the molar ratio of metal 1 to metal 2(M1:M2) is typically in the range of from about 25:1 to about 1:25 orfrom about 25:1 to about 2:1 or from about 20:1 to about 5:1.

The contacting step is typically carried out at a temperature in therange of from about 50° C. to about 150° C., or from about 80° C. toabout 130° C. In one embodiment, the hydrogen pressure during thecontacting step is in the range of from about 50 psig to about 2000psig. In another embodiment, the hydrogen pressure is in the range offrom about 100 psig to about 1500 psig. In a further embodiment, thehydrogen pressure is in the range of from about 200 psig to about 1000psig.

The contacting step is typically carried out in an organic solvent, suchas, for example, an alcohol, an ester, an ether, or a mixture thereof.Exemplary alcohols include, for example, ethanol, n-propanol,isopropanol, n-butanol, t-butanol, iso-butanol, sec-butanol, and thelike.

Exemplary esters include, for example, methyl acetate, ethyl acetate,propyl acetate, butyl acetate, and the like. Exemplary ethers include,for example, dioxane, dioxolane, glyme, diglyme, triglyme andtetraglyme. In one embodiment, the organic solvent contains less thanabout 25 wt % water. In another embodiment, the organic solvent containsless than about 10 wt % water. In another embodiment, the organicsolvent contains less than about 5 wt % water. In another embodiment,the organic solvent is substantially free of water.

In one embodiment BHMF is generated from U/F with at least about 90%selectivity. In another embodiment, BHMF is generated from HMF with atleast 95% selectivity. In some embodiments, BHMF is generated from IMFwith at least 99% selectivity.

In some embodiments, at least about 85% of IMF is converted to BHMF. Incertain embodiments, at least about 90% HMF is converted to BHMF. Inother embodiments, at least 95% about HMF is converted to BHMF. Infurther embodiments, at least about 99% HMF is converted to BHMF.

In one embodiment, the present invention provides a process forproducing bis-hydroxymethyltetrahydrofuran (BHMTHF) from2,5-bis-hydroxymethylfuran (BHMF), the method comprising:

contacting BHMF with hydrogen in the presence of a heterogeneoushydrogenation catalyst comprising a porous shaped metal-carbon productof the present invention to form BHMTHF, wherein the metal component ofthe metal-carbon product is selected from the group consisting of Ni,Co, Cu, Ag, Pd, Pt, Ru, and combinations thereof. In some embodiments,the metal component is selected from the group consisting of Ni, Co, Pd,Ru, and Pt. In certain embodiments, the metal component is selected fromthe group consisting of Ni, Pd, Co, and Pt. In other embodiments, themetal component is a combination of metals, such as a combinationselected from the group consisting of Co and Cu; Ni and Cu, Ru and Cu;Ag and Ni; Ag and Co; Ag and Ru; and Cu, Co, and Ni. Typically, themetal component is Ni.

The porous shaped metal-carbon product typically comprises the metalcomponent at a loading in the range of from about 0.5 wt % to about 99wt %. In some embodiments, the loading is in the range of from about0.01 wt % to about 25 wt %, or in the range of from about 0.1 wt % toabout 20 wt %, or in the range of from about 0.1 wt % to about 18 wt %.When the composite comprises two different metal species, M1 and M2, themolar ratio of metal 1 to metal 2 (M1:M2) is typically in the range offrom about 25:1 to about 1:25 or from about 25:1 to about 2:1 or fromabout 20:1 to about 5:1.

The contacting step is typically carried out at a temperature in therange of from about 80° C. to about 150° C., or from about 80° C. toabout 130° C. In one embodiment, the hydrogen pressure during thecontacting step is in the range of from about 50 psig to about 2000psig. In another embodiment, the hydrogen pressure is in the range offrom about 100 psig to about 1500 psig. In a further embodiment, thehydrogen pressure is in the range of from about 200 psig to about 1000psig.

The contacting step is typically carried out in an organic solvent, suchas, for example, an alcohol, an ester, an ether, or a mixture thereof.Exemplary alcohols include, for example, ethanol, n-propanol,isopropanol, n-butanol, t-butanol, iso-butanol, sec-butanol, and thelike. Exemplary esters include, for example, methyl acetate, ethylacetate, propyl acetate, butyl acetate, and the like. Exemplary ethersinclude, for example, dioxane, dioxolane, glyme, diglyme, triglyme andtetraglyme. In one embodiment, the organic solvent contains less thanabout 25 wt % water. In one embodiment, the organic solvent is a mixtureof 90% organic solvent and 10% water (v/v). In another embodiment, theorganic solvent contains less than about 10 wt % water. In anotherembodiment, the organic solvent contains less than about 5 wt % water.In another embodiment, the organic solvent is substantially free ofwater.

In one embodiment BHMTHF is generated from BHMF with at least about 80%selectivity. In some embodiments BHMTHF is generated from BHMF with atleast about 85% or at least about 90% selectivity. In anotherembodiment, BHMTHF is generated from BHMF with at least about 95%selectivity. In some embodiments, BHMTHF is generated from BHMF with atleast 99% selectivity.

In some embodiments, at least about 85% of BHMF is converted to BHMTHF.In certain embodiments, at least about 90% BHMF is converted to BHMTHF.In other embodiments, at least 95% about BHMF is converted to BHMTHF. Infurther embodiments, at least about 99% BHMF is converted to BHMTHF. Theconversion of BHMF to BHMTHF using a heterogeneous hydrogenationcatalyst that is a porous, shaped Ni-carbon product is illustrated inExample 5.

In another embodiment, the present invention provides a process forproducing a C₃-C₆ diol from a corresponding C₃-C₆ polyol, the methodcomprising:

contacting a C₃-C₆ polyol with hydrogen in the presence of ahydrodeoxygenation catalyst comprising a porous, shaped metal-carbonproduct of the present invention to form a corresponding C₃-C₆ diol,wherein the metal component of the porous, shaped metal-carbon productis a metal selected from the group consisting of Pd, Pt, Ir, Mo, W, V,Mn, Re, Zr, Ni, Cu, La, Sm, Y, Zn, Cr, Ge, Sn, Ti, Au, Rh, Co, andcombinations thereof. In some embodiments, the metal component isselected from the group consisting of Pt, W, and Mo. In certainembodiments, the metal is selected from the group consisting of Pt andW. In other embodiments, the metal is W.

The porous, shaped metal-carbon products typically comprises the metalcomponent at a loading in the range of from about 0.5 wt % to about 10wt %. In some embodiments, the loading is in the range of from about 0.2wt % to about 10 wt %, or in the range of from about 0.2 wt % to about 8wt %, or in the range of from about 0.2 wt % to about 5 wt %. In someembodiments, the total weight of the metal component is less than about4 wt % of the total weight of the porous, shaped metal-carbon product.When the product comprises two different species of metal components, M1and M2, the molar ratio of metal 1 to metal 2 (M1:M2) is typically inthe range of from about 20:1 to about 1:10 or from about 10:1 to about1:5 or from about 8:1 to about 1:2.

In some embodiments, the C₃-C₆ diol is selected from the groupconsisting of 1,5-pentanediol and 1,6-hexanediol. The C₃-C₆ diol may beproduced directly, or indirectly via one or more intermediates, from aC₃-C₆ polyol that is selected from the group consisting of1,2,6-hexanetriol, 1,2,5-pentanetriol, 2H-tetrahydropyran-2-methanol,tetrahydrofuran-2,5-dimethanol, furan-2,5-dimethanol,2,5-dihydrofuran-2,5-dimethanol, levoglucosenone, levoglucosan,levoglucosenol, 1,6-anhydro-3,4-dideoxy-p-D-pyranose-2-one, isosorbide,hydroxymethylfurfural, sorbitol, glucose, fructose, xylitol,3,4-dihydro-2H-pyran-2-carbaldehyde, 1,2,5,6-hexanetetraol,1,2,3,5,6-hexanepentanol, 1,5-anhydro-3,4-dideoxyhexitol,5-hydroxy-2H-tetrahydropyran-2 methanol, furfural, furfuryl alcohol,tetrahydrofurfuryl alcohol, a pentose, NS a hexose. Indirect productionof the C₃-C₆ diol may occur via an intermediate, such as, for example,furan dimethanol, tetrahydrofuran dimethanol,tetrahydropyran-2-methanol, levoglucosanol, furfuryl alcohol, and thelike.

The conversion of the C3-C6 polyol to the corresponding C3-C6 diol canbe conducted in the presence of a solvent. Solvents suitable for use inconjunction with the conversion of the C3-C6 polyol to the correspondingC3-C6 diol in the presence of the catalysts of the present inventioninclude, for example, eater, alcohols, esters, ethers, ketones, ormixtures thereof. In various embodiments, the preferred solvent iswater.

In an exemplary process, the C₃-C₆ polyol is 1,2,6-hexanetriol (HTO) andthe C₃-C₆ diol is 1,6-hexanediol (HDO). Typically, metal component ofthe porous shaped metal-carbon product is a metal selected from thegroup consisting of Mo, W, and a mixture thereof. More typically, theporous, shaped metal-carbon product has a second metal deposited thereon(on the internal and external surfaces). Typically, the shapedmetal-carbon product is a porous shaped W-carbon product having platinumdeposited thereon (on the internal and external surfaces).

In one embodiment, the contacting step is carried out at a temperaturein the range of from about 80° C. to about 200° C. In anotherembodiment, the contacting step is carried out at a temperature in therange of from about 100° C. to about 180° C. Typically, the hydrogenpressure during the contact step is in the range of from about 200 psigto about 5000 psig, in the range of from about 200 psig to about 4000psig, in the range of from about 200 psig or 500 psig to about 3000psig. In other embodiments the hydrogen pressure is in the range of fromabout 200 psig or 500 psig to about 2000 psig.

In one embodiment, the desired C₃-C₆ diol is generated from the C₃-C₆diol with at least about 80% selectivity. In another embodiment, thedesired C₃-C₆ diol is generated from the C₃-C₆diol with at least about81%, at least about 82%, at least about 83%, at least about 84%, atleast about 85%, at least about 86%, at least about 87%, at least about88%, at least about 89%, at least about 90%, at least about 91%, atleast about 92%, at least about 93%, at least about 94%, at least about95%, at least about 96%, at least about 97%, at least about 98%, or atleast about 99% selectivity. In some embodiments, at least about 25% ofthe C₃-C₆ polyol is converted to the desired C₃-C₆ diol. In certainembodiments, at least about 30% of the C₃-C₆ polyol is converted to thedesired C₃-C₆ diol. In other embodiments, at least about 35%, at leastabout 40%, at least about 45%, at least about 50%, at least about 55%,at least about 60%, at least bout 65%, at least about 70%, at leastabout 75%, at least about 80%, at least about 85%, at least about 90%,or at least about 95% of the C₃-C₆ polyol is converted to the desiredC₃-C₆ diol. In a specific embodiment, the C₃-C₆ polyol is1,2,6-hexanetriol and the C₃-C₆ diol is 1,6,-hexanediol.

In another embodiment, the present invention provides a process for theselective amination of 1,6-hexanediol (HDO) to 1,6-hexamethylenediamine(HMDA) comprising contacting the 1,6-hexanediol with an amine in thepresence of an amination catalyst comprising a porous, shapedmetal-carbon product of the present invention, wherein the metalcomponent of the porous, shaped metal-carbon product is selected fromthe group consisting of Ni, Ru, and Rh. Typically, the metal componentis Ni. In some embodiments of this process, Ru and/or Rh are depositedas a second metal (or mixture of metals) on the porous, shapedmetal-carbon product. Typically, the total weight of metal(s) is fromabout 0.1% to about 10%, from about 1% to about 6%, or from about 1% toabout 5% of the total weight of the catalyst composition.

In this process, when both Ru and Rh are employed, the molar ratio of Ruto Rh is important. A by-product of processes for converting HDO to HMDAis pentylamine. Pentylamine is an off path by-product of the conversionof HDO to HMDA that cannot be converted to HMDA or to an intermediatewhich can, on further reaction in the presence of the catalysts of thepresent invention, be converted to HMDA. However, the presence of toomuch rhodium can have an adverse effect on the yield of HMDA per unitarea time (commonly known as space time yield, or STY). Therefore, themolar ratio of Ru:Rh should be maintained in the range of from about20:1 to about 4:1. In various embodiments, the Ru:Rh molar ratio is inthe range of from about 10:1 to about 4:1 or from about 8:1 to about4:1. In some embodiments, the Ru:Rh molar ratio of from about 8:1 toabout 4:1 produces HMDA in at least 25% yield with an HMDA/pentylamineratio of at least 20:1, at least 25:1, or at least 30:1.

In accordance with the present invention, HDO is converted to HMDA byreacting HDO with an amine, e.g., ammonia, in the presence of theporous, shaped metal-carbon products of the present invention.Generally, in some embodiments, the amine may be added to the reactionin the form of a gas or liquid. Typically, the molar ratio of ammonia toHDO is at least about 40:1, at least about 30:1, or at least about 20:1.In various embodiments, it is in the range of from about 40:1 to about5:1, from about 30:1 to about 10:1. The reaction of HDO with amine inthe presence of the catalysts of the present invention is carried out ata temperature less than or equal to about 200° C. In variousembodiments, the catalyst is contacted with HDO and amine at atemperature less than or equal to about 100° C. In some embodiments, thecatalyst is contacted with HDO and amine at a temperature in the rangeof about 100° C. to about 180° C. or about 140° C. to about 180° C.

Generally, in accordance with the present invention, the reaction isconducted at a pressure not exceeding about 1500 psig. In variousembodiments, the reaction pressure is in the range of about 200 psig toabout 1500 psig. In other embodiments, and a pressure in the range ofabout 400 psig to about 1200 psig. In certain preferred embodiments, thepressure in the range of about 400 psig to about 1000 psig. In someembodiments, the disclosed pressure ranges includes the pressure of NH₃gas and an inert gas, such as N₂. In some embodiments, the pressure ofNH₃ gas is in the range of about 50-150 psig and an inert gas, such asN₂ is in the range of about 700 psig to about 1450 psig.

In some embodiments, the catalyst is contacted with HDO and ammonia at atemperature in the range of about 100° C. to about 180° C. and apressure in the range of about 200 psig to about 1500 psig. In otherembodiments, the catalyst is contacted with HDO and ammonia at atemperature in the range of about 140° C. to about 180° C. and apressure in the range of about 400 psig to about 1200 psig. In someembodiments, the disclosed pressure ranges includes the pressure of NH₃gas and an inert gas, such as N₂. In some embodiments, the pressure ofNH₃ gas is in the range of about 50-150 psig and an inert gas, such asN₂ is in the range of about 500 psig to about 1450 psig.

The process of the present invention may be carried out in the presenceof hydrogen. Typically, in those embodiments in which the HDO and amineare reacted in the presence of hydrogen and the catalyst of the presentinvention, the hydrogen partial pressure is equal to or less than about100 psig.

The conversion of HDO to HMDA can also be conducted in the presence of asolvent. Solvents suitable for use in conjunction with the conversion ofHDO to HMDA in the presence of the catalysts of the present inventionmay include, for example, water, alcohols, esters, ethers, ketones, ormixtures thereof. In various embodiments, the preferred solvent iswater.

The chemocatalytic conversion of HDO to HMDA is likely to produce one ormore by-products such as, for example, pentylamine and hexylamine.By-products which are subsequently convertible to HMDA by furtherreaction in the presence of catalysts of the present invention areconsidered on-path by-products. Other by-products such as, for example,pentylamine and hexylamine are considered off path by-products for thereasons above discussed. In accordance with the present invention, atleast 20%, at least 30%, at least 40%, at least 50%, at least 60%, or atleast 70% of the product mixture resulting from a single pass reactionof HDO with amine (e.g., ammonia) in the presence of the catalysts ofthe present invention is HMDA.

The resulting product mixture may be separated into one or more productsby any suitable methods known in the art. In some embodiments, theproduct mixture can be separated by fractional distillation undersubatmospheric pressures. For example, in some embodiments, HMDA can beseparated from the product mixture at a temperature between about 180°C. and about 220° C. The HDO may be recovered from any remaining otherproducts of the reaction mixture by one or more conventional methodsknown in the art including, for example, solvent extraction,crystallization or evaporative processes. The on-path by-products can berecycled to the reactor employed to produce the product mixture or, forexample, supplied to a second reactor in which the on path by-productsare further reacted with ammonia in the presence of the catalysts of thepresent invention to produce additional HMDA.

One series of catalytic applications that the porous, shapedmetal-carbon products of the present invention are suited for is theselective oxidation of a hydroxyl group to a carboxyl group in a liquidor gaseous reaction medium. An exemplary reaction is the selectiveoxidation of an aldose to an aldaric acid. Aldoses include, for example,pentoses and hexoses (i.e., C-5 and C-6 monosaccharides). Pentosesinclude ribose, arabinose, xylose, and lyxose, and hexoses includeglucose, allose, altrose, mannose, gulose, idose, galactose, and talose.Accordingly, in various embodiments, the present invention is alsodirected to a process for the selective oxidation of an aldose to analdaric acid comprising reacting the aldose with oxygen in the presenceof an oxidation catalyst comprising a porous, shaped metal-carbonproduct of the present invention to form the aldaric acid. Typically,the porous, shaped metal-carbon product is a base metal-carbon productwith a noble metal, e.g., platinum, deposited thereon (i.e., on externaland internal surfaces). More typically, the nobel metal is a mixture ofplatinum and gold. Often the base metal component of the basemetal-carbon product is tungsten.

In a specific embodiment, the present invention provides a process forthe selective oxidation of glucose to glucaric acid comprisingcontacting the glucose with oxygen in the presence of an oxidationcatalyst comprising a porous, shaped metal-carbon product as describedherein to form glucaric acid. Typically, the porous, shaped metal-carbonproduct is a base metal-carbon product with a noble metal, e.g.,platinum, deposited thereon (i.e., on external and internal surfaces).More typically, the nobel metal is a mixture of platinum and gold. Oftenthe base metal component of the base metal-carbon product is tungsten.The conversion of glucose to glucaric acid using a Au—Pt on a porous,shaped W-carbon product is described in Example 14.

U.S. Pat. No. 8,669,397, the entire contents of which are incorporatedherein by reference, discloses various catalytic processes for theoxidation of glucose to glucaric acid. In general, glucose may beconverted to glucaric acid in high yield by reacting glucose with oxygen(e.g., air, oxygen-enriched air, oxygen alone, or oxygen with otherconstituents substantially inert to the reaction) in the presence of anoxidation catalyst according to the following reaction:

The oxidation can be conducted in the absence of added base (e.g., KOH)or where the initial pH of the reaction medium and/or the pH of reactionmedium at any point in the reaction is no greater than about 7, nogreater than 7.0, no greater than about 6.5, or no greater than about 6.The initial pH of the reaction mixture is the pH of the reaction mixtureprior to contact with oxygen in the presence of an oxidation catalyst.In fact, catalytic selectivity can be maintained to attain glucaric acidyield in excess of about 30%, about 40%, about 50%, about 60% and, insome instances, attain yields in excess of 65% or higher. The absence ofadded base advantageously facilitates separation and isolation of theglucaric acid, thereby providing a process that is more amenable toindustrial application, and improves overall process economics byeliminating a reaction constituent. The “absence of added base” as usedherein means that base, if present (for example, as a constituent of afeedstock), is present in a concentration which has essentially noeffect on the efficacy of the reaction; i.e., the oxidation reaction isbeing conducted essentially free of added base. The oxidation reactioncan also be conducted in the presence of a weak carboxylic acid, such asacetic acid, in which glucose is soluble. The term “weak carboxylicacid” as used herein means any unsubstituted or substituted carboxylicacid having a pKa of at least about 3.5, more preferably at least about4.5 and, more particularly, is selected from among unsubstituted acidssuch as acetic acid, propionic acid or butyric acid, or mixturesthereof.

The oxidation reaction may be conducted under increased oxygen partialpressures and/or higher oxidation reaction mixture temperatures, whichtends to increase the yield of glucaric acid when the reaction isconducted in the absence of added base or at a pH below about 7.Typically, the partial pressure of oxygen is at least about 15 poundsper square inch absolute (psia) (104 kPa), at least about 25 psia (172kPa), at least about 40 psia (276 kPa), or at least about 60 psia (414kPa). In various embodiments, the partial pressure of oxygen is up toabout 1,000 psia (6895 kPa), more typically in the range of from about15 psia (104 kPa) to about 500 psia (3447 kPa), from about 75 psia (517kPa) to about 500 psia (3447 kPa), from about 100 psia (689 kPa) toabout 500 psia (3447 kPa), from about 150 psia (1034 kPa) to about 500psia (3447 kPa). Generally, the temperature of the oxidation reactionmixture is at least about 40° C., at least about 60° C., at least about70° C., at least about 80° C., at least about 90° C., at least about100° C., or higher. In various embodiments, the temperature of theoxidation reaction mixture is from about 40° C. to about 200° C., fromabout 60° C. to about 200° C., from about 70° C. to about 200° C., fromabout 80° C. to about 200° C., from about 80° C. to about 180° C., fromabout 80° C. to about 150° C., from about 90° C. to about 180° C., orfrom about 90° C. to about 150° C.

Oxidation of glucose to glucaric acid can also be conducted in theabsence of nitrogen as an active reaction constituent. Some processesemploy nitrogen compounds such as nitric acid as an oxidant. The use ofnitrogen in a form in which it is an active reaction constituent, suchas nitrate or nitric acid, results in the need for NO_(x) abatementtechnology and acid regeneration technology, both of which addsignificant cost to the production of glucaric acid from these knownprocesses, as well as providing a corrosive environment which maydeleteriously affect the equipment used to carry out the process. Bycontrast, for example, in the event air or oxygen-enriched air is usedin the oxidation reaction of the present invention as the source ofoxygen, the nitrogen is essentially an inactive or inert constituent.Thus, an oxidation reaction employing air or oxygen-enriched air is areaction conducted essentially free of nitrogen in a form in which itwould be an active reaction constituent.

Suitable methods for depositing platinum and gold, includingidentification of appropriate precursors are described in U.S. PatentApplication Publication 2011/0306790, which is incorporated herein byreference. This publication describes various oxidation catalystscomprising a catalytically active component comprising platinum andgold, which are useful for the selective oxidation of compositionscomprised of a primary alcohol. When platinum is employed, typically themass ratio of glucose to platinum is from about 10:1 to about 1000:1,from about 10:1 to about 500:1, from about 10:1 to about 200:1, or fromabout 10:1 to about 100:1.

In another series of chemical transformations that the porous, shapedmetal-carbon products are suited for use as hydrodeoxygenation catalystsfor the hydrodeoxygenation of carbon-hydroxyl groups to carbon-hydrogengroups in a liquid or gaseous reaction medium. For example, one seriesof chemical transformation that the catalyst compositions of the presentinvention are especially suited for is the selective halide-promotedhydrodeoxygenation of an aldaric acid or salt, ester, or lactone thereofto a dicarboxylic acid. Accordingly, porous, shaped metal-carbonproducts of the present invention as described herein can be utilized ashydrodeoxygenation catalysts. As such, the present invention is alsodirected to a process for the selective halide promotedhydrodeoxygenation of an aldaric acid comprising contacting the aldaricacid or salt, ester, or lactone thereof with hydrogen in the presence ofa halogen-containing compound and a hydroxygenation catalyst comprisinga porous, shaped metal-carbon product of the present invention to form adicarboxylic acid. Typically, the porous, shaped metal-carbon product isa porous, shaped base metal-carbon product having at least one noblemetal deposited thereon (on the exterior and interior surfaces).Typically, the noble metal is selected from the group consisting of Ru,Rh, Pd, Pt, Au, Ag, Os, Ir, and combinations thereof. The metalcomponent of the porous, shaped metal-carbon product is typically ametal selected from the group consisting of Co, Ni, Ti, V, Cr, Mn, Fe,Cu, Mo, W, and combinations thereof.

The hydrodeoxygenation catalysts of the present invention may beemployed in the selective halide-promoted hydrodeoxygenation of glucaricacid or salt, ester, or lactone thereof to adipic acid. U.S. Pat. No.8,669,397, referenced above and incorporated herein by reference,describes the chemocatalytic processes for the hydrodeoxygenation ofglucaric acid to adipic acid.

Adipic acid or salts and esters thereof may be prepared by reacting, inthe presence of a hydrodeoxygenation catalyst and a halogen source,glucaric acid or salt, ester, or lactone thereof, and hydrogen,according to the following reaction:

In the above reaction, glucaric acid or salt, ester, or lactone thereofis converted to an adipic acid product by catalytic hydrodeoxygenationin which carbon-hydroxyl groups are converted to carbon-hydrogen groups.In various embodiments, the catalytic hydrodeoxygenation ishydroxyl-selective wherein the reaction is completed without substantialconversion of the one or more other non-hydroxyl functional group of thesubstrate.

The halogen source may be in a form selected from the group consistingof ionic, molecular, and mixtures thereof. Halogen sources includehydrohalic acids (e.g., HCl, HBr, HI and mixtures thereof; preferablyHBr and/or HI), halide salts, (substituted or unsubstituted) alkylhalides, or molecular (diatomic) halogens (e.g., chlorine, bromine,iodine or mixtures thereof, preferably bromine and/or iodine). Invarious embodiments the halogen source is in diatomic form, hydrohalicacid, or halide salt and, more preferably, diatomic form or hydrohalicacid. In certain embodiments, the halogen source is a hydrohalic acid,in particular hydrogen bromide.

Generally, the molar ratio of halogen to the glucaric acid or salt,ester, or lactone thereof is about equal to or less than about 1. Invarious embodiments, the mole ratio of halogen to the glucaric acid orsalt, ester, or lactone thereof is typically from about 1:1 to about0.1:1, more typically from about 0.7:1 to about 0.3:1, and still moretypically about 0.5:1.

Generally, the reaction allows for recovery of the halogen source andcatalytic quantities (where molar ratio of halogen to the glucaric acidor salt, ester, or lactone thereof is less than about 1) of halogen canbe used, recovered and recycled for continued use as a halogen source.

Generally, the temperature of the hydrodeoxygenation reaction mixture isat least about 20° C., typically at least about 80° C., and moretypically at least about 100° C. In various embodiments, the temperatureof the hydrodeoxygenation reaction is conducted in the range of fromabout 20° C. to about 250° C., from about 80° C. to about 200° C., fromabout 120° C. to about 180° C., or from about 140° C. to 180° C.Typically, the partial pressure of hydrogen is at least about 25 psia(172 kPa), more typically at least about 200 psia (1379 kPa) or at leastabout 400 psia (2758 kPa). In various embodiments, the partial pressureof hydrogen is from about 25 psia (172 kPa) to about 2500 psia (17237kPa), from about 200 psia (1379 kPa) to about 2000 psia (13790 kPa), orfrom about 400 psia (2758 kPa) to about 1500 psia (10343 kPa).

The hydrodeoxygenation reaction may be conducted in the presence of asolvent.

Solvents suitable for the selective hydrodeoxygenation reaction includewater and carboxylic acids, amides, esters, lactones, sulfoxides,sulfones and mixtures thereof. Preferred solvents include water,mixtures of water and weak carboxylic acid, and weak carboxylic acid. Apreferred weak carboxylic acid is acetic acid.

Embodiments of the invention include the following:

1. A process for preparing a porous, shaped metal-carbon product, theprocess comprising:

mixing a carbonaceous material with water, a water-soluble organicbinder, and a (first) metal precursor to form a metal-carbon mixture,wherein the metal precursor is a compound selected from the groupconsisting of a metal carbonate, a metal oxide, a metal hydroxide, asalt of a metal acid, a heteropoly acid, a metal carboxylate, hydratesthereof, and a mixture thereof;

shaping the metal-carbon mixture to form a green shaped metal-carbonproduct; and

heating the green shaped metal-carbon product to a carbonizationtemperature to produce a carbonized, shaped metal-carbon productcomprising a plurality of pores.

2. The process of embodiment 1, wherein the metal precursor is a metalcarbonate or hydrate thereof.

3. The process of embodiment 1, wherein the metal precursor is a metaloxide or hydrate thereof.

4. The process of embodiment 1, wherein the metal precursor is a metalhydroxide or hydrate thereof.

5. The process of embodiment 1, wherein the metal precursor is a salt ofa metal acid or hydrate thereof.

6. The process of embodiment 1, wherein the metal precursor is aheteropoly acid or hydrate thereof.

7. The process of embodiment 1, wherein the metal precursor is acarboxylate of a metal acid or hydrate thereof.

8. The process of any of embodiments 1-7, wherein the metal precursorcomprises a metal that is a base metal.

9. The process of any of embodiments 1-7, wherein the metal precursorcomprises a metal selected from the group consisting of Cu, Pb, Ni, Zn,Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge, V, Ga,Hf, In, Nb, Rh, Tl, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and combinationsthereof.

10. The process of embodiment 9, wherein the metal precursor comprises ametal selected from the group consisting of Cu, Pb, Ni, Zn, Fe, Mo, Al,Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb,Rh, Tl, and combinations thereof.

11. The process of embodiment 10, wherein the metal precursor comprisesa metal selected from the group consisting of Ni, Co, W, Nb, Mo, andcombinations thereof.

12. The process of any of embodiments 1-7, wherein the metal precursoris capable of being decomposed and reduced to a metal at a temperaturein the range of from about 250° C. to about 1,000° C.

13. The process of any of embodiments 1-2 and 8-11, wherein the metalprecursor is a nickel carbonate or hydrate thereof.

14. The process of any of embodiments 1, 5, and 8-11, wherein the metalprecursor is ammonium metatungstate hydrate.

15. The process of any of embodiments 1-12, wherein the metal precursoris water insoluble.

16. The process of any of embodiments 1-12, wherein the metal precursoris water soluble.

17. The process of any of embodiments 1-16, wherein the metal precursoris present in the metal-carbon mixture in a quantity in the range offrom about 0.1 wt % to about 90 wt %.

18. The process of embodiment 17, wherein the metal precursor is presentin the metal-carbon mixture in a quantity in the range of from about 5wt % to about 70 wt %.

19. The process of embodiment 18, wherein the metal precursor is presentin the metal-carbon mixture in a quantity in the range of from about 10wt % to about 70 wt %.

20. The process of embodiment 18, wherein the metal precursor is presentin the metal-carbon mixture in a quantity in the range of from about 5wt % to about 60 wt %.

21. The process of embodiment 18, wherein the metal precursor is presentin the metal-carbon mixture in a quantity in the range of from about 10wt % to about 60 wt %.

22. The process of embodiment 18, wherein the metal precursor is presentin the metal-carbon mixture in a quantity in the range of from about 15wt % to about 70 wt %.

23. The process of embodiment 22, wherein the metal precursor is presentin the metal-carbon mixture in a quantity in the range of from about 25wt % to about 60 wt %.

24. The process of embodiment 17, wherein the metal precursor is presentin the metal-carbon mixture in a quantity in the range of from about 0.1wt % to about 10 wt %.

25. The process of embodiment 24, wherein the metal precursor is presentin the metal-carbon mixture in a quantity in the range of from about 0.1wt % to about 5 wt %.

26. The process of embodiment 25, wherein the metal precursor is presentin the metal-carbon mixture in a quantity in the range of from about 0.5wt % to about 5 wt %.

27. The process of any of embodiments 1-26, wherein the carbonaceousmaterial is present in the metal-carbon mixture in a quantity in therange of from about 15 wt % to about 80 wt %.

28. The process of embodiment 27, wherein the carbonaceous material ispresent in the metal-carbon mixture in a quantity in the range of fromabout 20 wt % to about 60 wt %.

29. The process of embodiment 27, wherein the carbonaceous material ispresent in the metal-carbon mixture in a quantity in the range of fromabout 15 wt % to about 35 wt %.

30. The process of any of embodiments 1-29, wherein the water-solubleorganic binder and carbonaceous material are present in the metal-carbonmixture in a weight ratio of at least about 1:4, at least about 1:3, atleast about 1:2 at least about 1:1, or at least about 1.5:1.

31. The process of any of embodiments 1-30, wherein the binder ispresent in the metal-carbon mixture in a quantity in the range of fromabout 10 wt % to about 50 wt %.

32. The process of any of embodiments 1-31, wherein the water is presentin the metal-carbon mixture in a quantity that is not more than about80% by weight of the metal-carbon mixture.

33. The process of any of embodiments 1-32, wherein the water-solubleorganic binder is a water-soluble polymer.

34. The process of embodiment 33, wherein the water-soluble polymer is acarbohydrate.

35. The process of embodiment 34, wherein the carbohydrate is acellulose.

36. The process of any of embodiments 1-22, wherein the water-solubleorganic binder is a sugar.

37. The process of any of embodiments 1-32, wherein the organicwater-soluble binder is a mixture of a cellulose and a sugar.

38. The process of any of embodiments 1-37, wherein the mixing step iscarried out in a mixer selected from the group consisting of a mixmuller, a planetary mixer, a drum mixer, a pan mixer, a twin shaftmixer, and a cement mixer.

39. The process of any of embodiments 1-38, further comprising premixingtogether a subset of components selected from the group consisting ofthe water, the water-soluble organic binder, the carbonaceous material,and the metal precursor.

40. The process of embodiment 39, comprising premixing together thewater and the water-soluble organic binder to form a binder solution.

41. The process of embodiment 39, comprising premixing together thewater, water-soluble organic binder, and the metal precursor.

42. The process of embodiment 39, further comprising premixing togetherthe carbonaceous material and the metal precursor.

43. The process of any of embodiments 1-42 wherein the shaping stepcomprises a process selected from the group consisting of pressing,casting, injection molding, extruding, spreading, pelletizing,granulating, calandaring, and 3-D printing.

44. The process of embodiment 43, wherein the shaping step furthercomprises breaking the product of a process selected from the groupconsisting of pressing, casting, injection molding, extruding,spreading, pelletizing, granulating, calendering, and 3-D printing, intosmaller pieces.

45. The process of any of embodiments 1-44 further comprising drying themetal-carbon mixture to remove at least a portion of the water prior toheating the green, shaped metal-carbon product to the carbonizationtemperature.

46. The process of embodiment 45, wherein the drying is carried out at atemperature in the range of from about 20° C. to about 150° C., or fromabout 40° C. to about 120° C., or from about 60° C. to about 120° C.

47. The process of any of embodiments 1-46, wherein the carbonizationtemperature is in the range of from about 250° C. to about 1000° C., orfrom about 300 C to about 950° C., or from about 300 C to about 900° C.,or from about 350° C. to about 900° C., or from about 350° C. to about850° C. or from about 350° C. to about 800° C.

48. The process of any of embodiments 1-47, further comprisingcontacting the carbonized, shaped metal-carbon product with a reducingagent at a temperature in the range of from about 100° C. to about 600°C.

49. The process of any of embodiments 1-48, further comprising formingparticles of the carbonized, shaped metal-carbon product.

50. The process of any of embodiments 1-49, wherein the carbonized,shaped metal-carbon product comprises the metal in an amount in therange of from about 0.1 wt % to about 70 wt %.

51. The process of any of embodiments 1-50, wherein the carbonized,shaped metal-carbon product exhibits a catalytic activity.

52. The process of any of embodiments 1-51, wherein the carbonized,shaped metal-carbon product is electrically conductive.

53. The process of any of embodiments 1-52, wherein the carbonaceousmaterial is a carbon black.

54. The process of any of embodiments 1-52, wherein the carbonaceousmaterial is an activated carbon.

55. The process of any of embodiments 1-52, wherein the carbonaceousmaterial is a graphite.

56. The process of any of embodiments 1-52, wherein the carbonaceousmaterial is a mixture of any two or more materials selected from thegroup consisting of a carbon black, an activated carbon, and a graphite.

57. The process of any of embodiments 1-54 and 56, wherein thecarbonaceous material has a BET specific surface area of at least about20 m²/g.

58. The process of embodiment 57, wherein the carbonaceous material hasa BET specific surface area in the range of from about 20 m²/g to about500 m²/g.

59. The process of any of embodiments 1-53 and 57-58, wherein thecarbonized, shaped metal-carbon product comprises a pore volume, whereinfrom about 50% to about 95% of the pore volume is from pores having apore diameter in the range of from about 5 nm to about 100 nm, asmeasured by the BJH process on the basis of pores having a diameter offrom 1.7 nm to 100 nm.

60. The process of embodiment 1-53 and 57-59, wherein no more than about10% of the pore volume is from pores having a pore diameter less thanabout 10 nm.

61. The process of any of embodiments 1-53 and 57-60, wherein thecarbonized, shaped metal-carbon product comprises a specific pore volumeof pores having a diameter in the range of from 1.7 nm to 100 nm, asmeasured by the BJH process, that is from about 0.1 cm³/g to about 1.5cm³/g.

62. The process of any of embodiments 1-53 and 57-61, wherein thecarbonized, shaped metal-carbon product exhibits a radial piece crushstrength of greater than about 4.4 N/mm (1 lb/mm).

63. The process of any of embodiments 1-52 and 54, wherein thecarbonaceous material has a BET specific surface area in the range offrom about 550 m²/g to about 3500 m²/g.

64. The process of any of embodiments 1-63, further comprisingdepositing a second metal precursor on the surfaces of the carbonized,shaped metal-carbon product.

65. The process of embodiment 64, wherein the second metal precursorcomprises a metal that is different from the metal in the first metalprecursor.

66. The process of embodiment 65, wherein the second metal precursorcomprises a metal that is a noble metal.

67. The carbonized, shaped metal-carbon product of any of embodiments1-66.

68. A porous shaped metal-carbon product comprising a porous carbonmatrix and a metal component, wherein the metal component of the porous,shaped metal-carbon product is present at a metal loading of at leastabout 10 wt %.

69. The porous shaped metal-carbon product of embodiment 68, wherein themetal loading is at least about 11 wt %, at least about 12 wt %, atleast about 13 wt %, at least about 14 wt %, at least about 15 wt %, atleast about 16 wt %, at least about 17 wt %, at least about 18 wt %, atleast about 19 wt %, or at least about 20 wt %.

70. The product of any of embodiments 66-67, wherein the metal componentof the porous, shaped metal-carbon product is a base metal.

71. The product of any of embodiments 68-70, wherein the metal componentof the porous, shaped metal-carbon product is selected from the groupconsisting of Cu, Pb, Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr,Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb, Rh, Tl, Ru, Rh, Pd, Ag, Os, Ir,Pt, Au, and combinations thereof.

72. The product of embodiment 71, wherein the metal component of themetal-carbon product is selected from the group consisting of Cu, Pb,Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge,V, Ga, Hf, In, Nb, Rh, Tl, and combinations thereof.

73. The product of embodiment 72, wherein the metal component of themetal-carbon product is selected from the group consisting of Ni, Co, W,Nb, Mo, and combinations thereof.

74. The product of embodiment 73, wherein the metal component of themetal-carbon product is selected from the group consisting of Ni, W, andcombinations thereof.

75. The product of any of embodiments 67-74, further comprising a secondmetal deposited on the surfaces of the porous shaped metal-carbonproduct.

76. The product of embodiment 75, wherein the second metal is differentfrom the metal component of the metal-carbon product.

77. The porous shaped metal-carbon product of embodiment 76, wherein thesecond metal is a noble metal.

78. The porous shaped metal-carbon product of embodiment 77, wherein thenoble metal is selected from the group consisting of Pt and Au.

79. The porous shaped metal-carbon product of any of embodiments 67-78,wherein the product is catalytically active.

80. A process for producing bis-hydroxymethyltetrahydrofuran (BHMTHF)from 2,5-bis-hydroxymethylfuran (BHMF), the process comprising:

contacting BHMF with hydrogen in the presence of a heterogeneoushydrogenation catalyst comprising a porous shaped metal-carbon productto form BHMTHF, wherein the metal component of the metal-carbon productis selected from the group consisting of a Ni, Co, Cu, Ag, Pd, Pt, Ru,and combinations thereof.

81. The process of any of embodiment 80, wherein the metal component isNi.

82. The process of any of embodiments 80-81, wherein the metal componentis present at a metal loading in the range of from about 0.5 wt % toabout 99 wt %.

83. The process of any of embodiments 80-82, wherein the contacting stepis carried out at a temperature in the range of from about 80° C. toabout 150° C.

84. The process of any of embodiments 80-83, wherein the hydrogen ispresent at a pressure in the range of from about 50 psig to about 2000psig.

85. The process of any of embodiments 80-84, wherein the BHMTHF isproduced at a selectivity of at least about 90%.

86. The process of any of embodiments 80-85, wherein at least about 85%of BHMF is converted to BHMTHF.

87. A process for producing a C₃-C₆ diol from a corresponding C₃-C₆polyol, the process comprising:

contacting a C₃-C₆ polyol with hydrogen in the presence of ahydrodeoxygenation catalyst comprising a porous, shaped metal-carbonproduct to form a corresponding C₃-C₆ diol, wherein the metal componentof the metal-carbon product is selected from the group consisting of Pd,Pt, Ir, Mo, W, V, Mn, Re, Zr, Ni, Cu, La, Sm, Y, Zn, Cr, Ge, Sn, Ti, Au,Rh, Co, and combinations thereof.

88. The process of any of embodiments 87, wherein the metal component isNi.

89. The process of any of embodiments 87-88, wherein the metal componentis present at a metal loading in the range of from about 0.5 wt % toabout 10 wt %.

90. The process of any of embodiments 87-89, wherein the C₃-C₆ polyol isselected from the group consisting of 1,2,6-hexanetriol,1,2,5-pentanetriol, 2H-tetrahydropyran-2-methanol,tetrahydrofuran-2,5-dimethanol, furan-2,5-dimethanol,2,5-dihydrofuran-2,5-dimethanol, levoglucosenone, levoglucosan,levoglucosenol, 1,6-anhydro-3,4-dideoxy-p-D-pyranose-2-one, isosorbide,hydroxymethylfurfural, sorbitol, glucose, fructose, xylitol,3,4-dihydro-2H-pyran-2-carbaldehyde, 1,2,5,6-hexanetetraol,1,2,3,5,6-hexanepentanol, 1,5-anhydro-3,4-dideoxyhexitol,5-hydroxy-2H-tetrahydropyran-2 methanol, furfural, furfuryl alcohol,tetrahydrofurfuryl alcohol, a pentose, and a hexose.

91. The process of any of embodiments 87-90, wherein the C₃-C₆ diol isselected from the group consisting of 1,5-pentanediol and1,6-hexanediol.

92. The process of any of embodiments 87-91, wherein the porous shapedmetal-carbon product further comprises Pt deposited on the surfaces ofthe porous shaped metal-carbon product.

93. The process of any of embodiments 87-92, wherein the C₃-C₆ polyol is1,2,6-hexanetriol and the C₃-C₆ diol is 1,6-hexanediol.

94. The process of any of embodiments 87-93, wherein the contacting stepis carried out at a temperature in the range of from about 80° C. toabout 200° C.

95. The process of any of embodiments 87-94, wherein the hydrogen ispresent at a pressure in the range of from about 200 psig to about 3000psig.

96. The process of any of embodiments 87-95, wherein the C₃-C₆ diol isproduced at a selectivity of at least about 80%.

97. A process for producing 1,6-hexamethylenediamine (HMDA) from1,6-hexanediol (HDO), the process comprising:

contacting 1,6-hexanediol with an amine in the presence of an aminationcatalyst comprising a porous, shaped metal-carbon product to form HMDA,wherein the metal component of the porous, shaped metal-carbon productis a metal selected from the group consisting of Ni, Ru, and Rh.

98. A process for producing glucaric acid from glucose, the processcomprising:

contacting glucose with oxygen in the presence of an oxidation catalystcomprising a porous, shaped metal-carbon product to form glucaric acid,wherein the metal component of the porous, shaped metal-carbon productis a base metal.

99. The process of embodiment 98, wherein the porous, shapedmetal-carbon product further comprises a noble metal deposited thereon.

100. A process for producing a dicarboxylic acid from an aldaric acid,or salt, ester, or lactone thereof, the process comprising:

contacting an aldaric acid, or salt, ester or lactone thereof withhydrogen in the presence of a halogen-containing compound and ahydroxygenation catalyst comprising a porous, shaped metal-carbonproduct of the present invention to form a dicarboxylic acid, whereinthe metal component of the porous, shaped metal-carbon product is a basemetal.

101. The process of embodiment 100, wherein the porous, shapedmetal-carbon product further comprises a noble metal deposited thereon.

102. A process for producing 2,5-bis-hydroxymethylfuran (BHMF) from5-hydroxymethylfurfural (HMF), the method comprising:

contacting HMF with hydrogen in the presence of a hydrogenation catalystcomprising a porous, shaped metal-carbon product of the presentinvention to form BHMF, wherein the metal component of the porous,shaped metal-carbon product is selected from the group consisting of Ni,Zn, Co, Cu, Ag, Pt, Pd, Fe, Ru, Au, W, Sb, Bi, Pb, and combinationsthereof.

The foregoing and other aspects of the invention may be betterunderstood in connection with the following non-limiting examples.

EXAMPLES Example 1 Preparation of a 10% Ni-Carbon Catalyst

33.80 g Nickel carbonate, basic hydrate NiCO₃.2Ni(OH)₂ xH₂O (Mw 358.12x=3) from Sigma-Aldrich (SKU 544183) was added to an aqueous solution(250 g) containing 42.0 wt. % glucose (ADM Corn Processing, DextroseMonohydrate 99.7DE with 91.2255 wt % Glucose content) and 3.0 wt. %hydroxyethylcellulose from Sigma-Aldrich (SKU 54290, viscosity 80-125cP, 2% in H₂O at 20° C.) to form a suspension with stirring. 100 g ofcarbon black powder (Timcal Ensaco 250 g, 65 m²/g) was then added toabove suspension. The mixture was mixed in a laboratory muller, whichwas running for 2 hours to ensure good mixing and kneading of material.The material was then loaded into a 1″ Bonnot BB Gun Extruder andextrudated into spaghetti like strings with ca. 1.5 mm diameter at crosssection. These strings were dried under a dry air purge in a 120° C.oven overnight. Then they were treated at 800° C. for 2 hours with 30°C./min temperature ramp rate under continuous N₂ flow to produce carbonblack extrudates. Finally catalysts has been reduced at 430 C for 6 hrsin the forming gas flow (5% H₂, 95% N₂) and passivated with the gasmixture 0.1% 02 in N₂ for 2 hrs at room temperature.

Example 2 Preparation of a 15% Ni-Carbon Catalyst

54.65 g Nickel carbonate, basic hydrate NiCO₃.2Ni(OH)₂ xH₂O (Mw 358.12x=3) from Sigma-Aldrich (SKU 544183) was added to an aqueous solution(250 g) containing 42.0 wt. % glucose (ADM Corn Processing, DextroseMonohydrate 99.7DE with 91.2255 wt % Glucose content) and 3.0 wt. %hydroxyethylcellulose from Sigma-Aldrich (SKU 54290, viscosity 80-125cP, 2% in H₂O at 20° C.) to form a suspension with stirring. 100 g ofcarbon black powder (Timcal Ensaco 250 g, 65 m²/g) was then added toabove suspension and the mixture was mixed in a laboratory muller, whichwas running for 2 hours to ensure good mixing and kneading of material.The material was then loaded into a 1″ Bonnot BB Gun Extruder andextrudated into spaghetti like strings with ca. 1.5 mm diameter at crosssection. These strings were dried under a dry air purge in a 120° C.oven overnight. Then they were treated at 800° C. for 2 hours with 30°C./min temperature ramp rate under continuous N₂ flow to produce carbonblack extrudates. Finally catalysts has been reduced at 430 C for 6 hrsin the forming gas flow (5% H₂, 95% N₂)) and passivated with the gasmixture 0.1% 02 in N₂ for 2 hrs at room temperature.

Example 3 Preparation of 20% Ni-Carbon Catalyst

79.10 g Nickel carbonate, basic hydrate NiCO₃.2Ni(OH)₂ xH₂O (Mw 358.12x=3) from Sigma-Aldrich (SKU 544183) was added to an aqueous solution(250 g) containing 42.0 wt. % glucose (ADM Corn Processing, DextroseMonohydrate 99.7DE with 91.2255 wt % Glucose content) and 3.0 wt. %hydroxyethylcellulose from Sigma-Aldrich (SKU 54290, viscosity 80-125cP, 2% in H₂O at 20° C.) to form a suspension with stirring. 100 g ofcarbon black powder (Timcal Ensaco 250G, 65 m²/g) was then added toabove suspension and the mixture was mixed in a laboratory muller, whichwas running for 2 hours to ensure good mixing and kneading of material.The material was then loaded into a 1″ Bonnot BB Gun Extruder andextrudated into spaghetti like strings with ca. 1.5 mm diameter at crosssection. These strings were dried under a dry air purge in a 120° C.oven overnight. Then they were treated at 800° C. for 2 hours with 30°C./min temperature ramp rate under continuous N₂ flow to produce carbonblack extrudates. Finally catalysts has been reduced at 430 C for 6 hrsin the forming gas flow (5% H₂, 95% N₂)) and passivated with the gasmixture 0.1% 02 in N₂ for 2 hrs at room temperature.

Example 4 Preparation of Comparative Ni-Alumina Catalyst

25.6 g of Ni(NO₃)₂x6H₂O (Alfa-Aesar) was dissolved in 15 ml DI water. 6ml of this solution was added to 6 g of Alumina carrier (XA 31132,Saint-Gobain). Material was dried at 120° C., 2 hrs and calcined at 350°C. for 3 h. Then the material was reduced in forming gas (5% H₂, 95% N₂)for 6 hrs at temperature 430° C. and passivated with the gas mixture0.1% O₂ in N₂ for 2 hrs. Calculated Ni loading was 15.3 wt %.

Example 5 Catalytic Hydrogenation Activity Test

All catalysts including comparative example were tested in highthroughput mode in a HiP-HOSS reactor (see “High-ThroughputHeterogeneous Catalyst Research,” Howard W. Turner, Anthony F. Volpe Jr,and W. H. Weinberg, Surface Science 603 (2009) 1763-1769, which isincorporated herein by reference) according to following procedure. 20mg catalysts have been placed in 1 ml vials, filled with 0.2 ml of 0.4Msolution of BHMF (2,5 dimethanol furan) in solvent 90% i-PA+10% H₂O(v/v). The test was conducted at a temperature of 110° C. for 3 hrsunder hydrogen pressure 700 psi. Observed products were 2,5 BHMTHF (2,5dimethanol tetrahydrofuran) and 1,2,6 HTO (1,2,6-hexane triol). Theresults are provided in Table 1.

TABLE 1 Hydrogenation Activity BHMTHF BHMTHF 1,2,6-HTO Mass selectivity,% Example No. Catalyst Yield, % Yield, % Balance, % (BHMTHF) 1 10% Ni/C84 0 84 84 2 15% Ni/C 97 0 97 97 3 20% Ni/C 92 0 92 92 4  15.3% Ni/Al₂O₃91 7 99 92 (comparative)

The results indicate that Ni—C catalysts prepared according to thisinvention procedure possess good hydrogenation activity and selectivityfor double bond hydrogenation that is comparable to performance of Ni onalumina catalysts with similar Ni loading.

Example 6 Preparation of Tungsten Containing Carbon Black ExtrudatesUsing Carbon Black Powder and Carbohydrate Based Binders

200 g of carbon black powder (Timcal Ensaco 250G, 65 m²/g) was added toan aqueous solution (500 g) containing 42.0 wt. % glucose (ADM CornProcessing, Dextrose Monohydrate 99.7DE with 91.2255 wt % Glucosecontent), 3.0 wt. % hydroxyethylcellulose from Sigma-Aldrich (SKU 54290,viscosity 80-125 cP, 2% in H₂O at 20° C.), and 0.82 wt. % ammoniummetatungstate hydrate from Sigma-Aldrich (SKU 358975). The mixture wasmixed in a laboratory muller, which was running for 2 hours to ensuregood mixing and kneading of material. The material was then loaded intoa 1″ Bonnot BB Gun Extruder and extrudated into spaghetti like stringswith ca. 1.5 mm diameter at cross section. These strings were driedunder a dry air purge in a 120° C. oven overnight. Then they weretreated at 800° C. for 2 hours with 30° C./min temperature ramp rateunder continuous N₂ flow to produce carbon black extrudates. By usingother carbon black powders and carbohydrate binders with various amountof other tungsten containing species, different carbon black extrudateswere prepared in a similar manner.

Example 7 Preparation of Platinum on Tungsten Containing Carbon BlackExtrudates

15 g of tungsten containing carbon black extrudates from Example 6 wasdivided evenly into thirty 40 ml vials. A suitably concentrated aqueoussolution of Pt(NO₃)₂ (Heraeus) (ca. 4.3 wt % Pt) was added to thirtyvials and agitated to impregnate the support. The samples were dried inan oven at 60° C. for 3 hours under static air; then calcined at 360° C.under an air atmosphere for 2 hours with 5° C./min temperature ramprate. Mass loss of ca. 10% was recorded during the thermo-treatment,leading to the final catalyst metal content being approximately 5.9 wt %Pt and 1.2 wt % W.

Example 8 Catalytic Hydrodeoxygenation Activity Test

Reaction was conducted in a ½″ OD by 83 cm long 316 stainless steel tubewith co-current down-flow of gas and liquid. Catalyst bed was vibrationpacked with 1.0 mm glass beads at the top to approximately 40 cm depth,followed by catalyst (28.5 cm bed depth containing 10.0 g), then SiC atthe bottom to approximately 8 cm depth. Quartz wool plugs separated thecatalyst bed from the SiC.

The packed reactor tube was clamped in an aluminum block heater equippedwith PID controller at 120° C. Gas (hydrogen) and liquid flow of 0.4 M1,2,6-hexanetriol (Spectrum Chemical and TCI America) in water wasregulated by mass flow controller and HPLC pump, respectively. A backpressure regulator controlled reactor pressure at 1000 psig. Thecatalyst was tested for ca. 429 hours ToS under the above conditions.The liquid phase eluent was diluted with methanol and analyzed by gaschromatography with flame ionization detection. Table 2 describes thefixed bed reactor conditions and resulting catalyst performance.

TABLE 2 1,2,6-Hexanetriol to 1,6-Hexanediol 1,6-HDO ToS Flow 1,2,6-HTOYield 1,2-HDO 1,5-HDO 1-Hexanol 2-Hexanol (hours) (ml/min) Remaining (%Sel) Yield Yield Yield Yield 43 1 38% 51% (82%)  1% 1% 6% <1% 253 1 66%29% (87%) <1% 1% 1% <1% 319 0.5 54% 41% (88%) <1% 1% 3% <1% 427 0.5 62%34% (89%) <1% 1% 2% <1%

Example 9 Preparation of Tungsten Containing Carbon Black ExtrudatesUsing Carbon Black Powder and Carbohydrate Based Binders

200 g of carbon black powder (Timcal Ensaco 250G, 65 m²/g) was added toan aqueous solution containing 275 g water, 210 g glucose (ADM CornProcessing, Dextrose Monohydrate 99.7DE with 91.2255 wt % Glucosecontent), 15 g hydroxyethylcellulose from Sigma-Aldrich (SKU 54290,viscosity 80-125 cP, 2% in H₂O (20° C.)), and (Support ID b) 8.35 g;(Support ID “c”) 19.95 g; (Support ID “d”) 33.65 g of ammoniummetatungstate hydrate (“AMT”) from Sigma-Aldrich (SKU 358975). Themixture was mixed in a laboratory muller, which was running for 2 hoursto ensure good mixing and kneading of material. The material was thenloaded into a 1″ Bonnot BB Gun Extruder and extruded into spaghetti likestrings with ca. 1.5 mm diameter at cross section. These strings weredried under a dry air purge in a 120° C. oven overnight. Then they weretreated at 800° C. for 2 hours with 30° C./min temperature ramp rateunder continuous N₂ flow to produce carbon black extrudates.

Varying amounts of Tungsten (VI) oxide from Strem Chemicals (Lot25575500): (Support ID “e”) 0.92 g; (Support ID “f”) 1.86 g; (Support ID“g”) 3.76 g and 100 g of carbon black powder (Timcal Ensaco 250G, 65m²/g) were added to an aqueous solution containing 135 g water, 105 gglucose (ADM Corn Processing, Dextrose Monohydrate 99.7DE with 91.2255wt % Glucose content), 7.5 g hydroxyethylcellulose from Sigma-Aldrich(SKU 54290, viscosity 80-125 cP, 2% in H₂O (20° C.)). The mixture wasmixed in a laboratory muller, which was running for 2 hours to ensuregood mixing and kneading of material. The material was then loaded intoa 1″ Bonnot BB Gun Extruder and extruded into spaghetti like stringswith ca. 1.5 mm diameter at cross section. These strings were driedunder a dry air purge in a 120° C. oven overnight. Then they weretreated at 800° C. for 2 hours with 30° C./min temperature ramp rateunder continuous N₂ flow to produce carbon black extrudates.

Example 10 Preparation of Platinum on Tungsten Containing Carbon BlackExtrudates (Support ID b in Table 3)

15 g of tungsten containing carbon black extrudates (2 wt % W) fromExample 9 was divided evenly into thirty 40 ml vials. A suitablyconcentrated aqueous solution of Pt(N₃)₂ (Heraeus) was added to thirtyvials and agitated to impregnate the support. The samples were dried inan oven at 60° C. for 3 hours under static air; then calcined at 360° C.under an air atmosphere for 2 hours with 5° C./min temperature ramprate. The contents of the thirty vials were combined. Mass loss of ca.5% was recorded during the thermo-treatment, leading to the finalcatalyst metal content being approximately 5.1 wt % Pt and 2 wt % W. One0.25 g sample of the final catalyst was further thermally treated at 75°C. under a 5% hydrogen/95% nitrogen atmosphere for 3 hours with 5°C./min temperature ramp rate.

Example 11 Preparation of Platinum on Tungsten Containing Carbon BlackExtrudates (Support ID c-g in Table 3)

0.5 g of each of the tungsten containing carbon black extrudates fromExample 10 was divided evenly into one of five 40 ml vials. A suitablyconcentrated aqueous solution of Pt(N₃)₂ (Heraeus) was added to eachvial and agitated to impregnate the support. The samples were dried inan oven at 60° C. for 3 hours under static air; then calcined at 360° C.under an air atmosphere for 2 hours with 5° C./min temperature ramprate. 0.25 g sample of each of the above catalysts was further thermallytreated at 75° C. under a 5% hydrogen/95% nitrogen atmosphere for 3hours with 5° C./min temperature ramp rate.

Example 12 Testing of Platinum on Tungsten Containing Carbon BlackExtrudates in a Batch Reactor for the hydrodeoxygenation of1,2,6-hexanetriol to 1,6-hexanediol

These twelve extrudate catalysts were tested for 1,2,6-hexanetriol(Spectrum Chemical) reduction using the following catalyst testingprotocol. The extrudate catalysts were crushed. A small sample of eachcatalyst (ca. 10 mg) was weighed into glass vial inserts, followed byaddition of an aqueous 1,2,6-hexanetriol solution (200 μl of 0.8 M). Theglass vial inserts were loaded into a reactor and the reactor wasclosed. The atmosphere in the reactor was replaced with hydrogen andpressurized to 670 psig at room temperature. The reactor was heated to160° C. and maintained at 160° C. for 2.5 hours while vials were shaken.After 2.5 hours, shaking was stopped and reactor was cooled to 40° C.Pressure in the reactor was then slowly released. The glass vial insertswere removed from the reactor. The solutions were diluted with methanoland analyzed by gas chromatography with flame ionization detection. Theresults are summarized in Table 3.

TABLE 3 1,2,6-Hexanetriol to 1,6-Hexanediol Support 1,6-HDO Yield ID wt% W W Source Thermo-treatment (% Selectivity) b 2.0 AMT C: 360° C., 2hrs 32% (87%) c 4.6 AMT C: 360° C., 2 hrs 18% (82%) d 7.5 AMT C: 360°C., 2 hrs 21% (84%) e 0.5 WO₃ C: 360° C., 2 hrs 3% (64%) f 1.0 WO₃ C:360° C., 2 hrs 11% (71%) g 2.0 WO₃ C: 360° C., 2 hrs 9% (77%) b 2.0 AMTC: 360° C., 2 h + 38% (89%) R: 75° C., 3 hrs c 4.6 AMT C: 360° C., 2 h +23% (84%) R: 75° C., 3 hrs d 7.5 AMT C: 360° C., 2 h + 17% (81%) R: 75°C., 3 hrs e 0.5 WO₃ C: 360° C., 2 h + 4% (66%) R: 75° C., 3 hrs f 1.0WO₃ C: 360° C., 2 h + 9% (76%) R: 75° C., 3 hrs g 2.0 WO₃ C: 360° C., 2h + 14% (76%) R: 75° C., 3 hrs C—calcination conditions R—reductionconditions

Example 13 Preparation of Gold-Platinum on Tungsten Containing CrushedCarbon Black Extrudates

0.1 g of each of the tungsten containing carbon black extrudates fromExample 9 was placed in a 4 ml vials and crushed to powder. A suitablyconcentrated aqueous solution of NMe4AuO2 and PtO(NO3) was added to thesix vials and agitated to impregnate the support. The samples were driedin an oven at 60° C. for 3 hours under 5% hydrogen/95% nitrogenatmosphere; followed by further treatment at 350° C. for 3 hours with 5°C./min temperature ramp rate. Each catalysts' metal loading was ca. 0.51wt % Au; 0.93 wt % Pt.

Example 14 Testing of Gold-Platinum on Tungsten Containing CrushedCarbon Black Extrudates in a Batch Reactor for the Oxidation of Glucoseto Glucaric Acid

Six catalysts were tested for glucose (ADM) oxidation using thefollowing catalyst testing protocol. Catalyst (ca. 16 mg) were weighedinto glass vial inserts followed by addition of an aqueous glucosesolution (250 μl of 20 wt. %). The glass vial inserts were loaded into areactor and the reactor was closed. The atmosphere in the reactor wasreplaced with oxygen and pressurized to 150 psig at room temperature.Reactor was heated to 110° C. and maintained at 110° C. for 2 hourswhile vials were shaken. After 2 hours, shaking was stopped and reactorwas cooled to 40° C. Pressure in the reactor was then slowly released.The glass vial inserts were removed from the reactor. The solutions werediluted with water and analyzed by ion chromatography withCAD/connectivity detection. A summary of the results is provided inTable 4.

TABLE 4 Glucose to Glucaric Acid Yield Support Glucose Glucaric ID wt %W W Source Conversion Acid Yield  b* 2.0 AMT 88% 15% c 4.6 AMT 81% 12% d7.5 AMT 88% 19% e 0.5 WO₃ 82% 13% f 1.0 WO₃ 90% 17% g 2.0 WO₃ 94% 21%*12 mg of catalyst used

While preferred embodiments of the invention have been illustrated anddescribed, it will be appreciated that various changes can be madetherein without departing from the spirit and scope of the invention.

We claim:
 1. A porous shaped metal-carbon product comprising a porouscarbon matrix and a metal component, wherein the metal component of theporous, shaped metal-carbon product is present at a metal loading of atleast about 10 wt %.
 2. The product of claim 1, wherein the metalloading is at least about 15 wt %.
 3. The product of claim 1, whereinthe metal component of the porous, shaped metal-carbon product is a basemetal.
 4. The product of claim 1, wherein the metal component of theporous, shaped metal-carbon product is selected from the groupconsisting of Cu, Pb, Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr,Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb, Rh, Tl, Ru, Rh, Pd, Ag, Os, Ir,Pt, Au, and combinations thereof.
 5. The product of claim 1, wherein themetal component of the metal-carbon product is selected from the groupconsisting of Cu, Pb, Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr,Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb, Rh, Tl, and combinations thereof.6. The product of claim 1, wherein the metal component of themetal-carbon product is selected from the group consisting of Ni, Co, W,Nb, Mo, and combinations thereof.
 7. The product of claim 1, wherein themetal component of the metal-carbon product is selected from the groupconsisting of Ni, W, and combinations thereof.
 8. The product of claim1, further comprising a second metal deposited on the surfaces of theporous shaped metal-carbon product.
 9. The product of claim 8, whereinthe second metal is different from the metal component of themetal-carbon product.
 10. The product of claim 9, wherein the secondmetal is a noble metal.
 11. The product of claim 10, wherein the noblemetal is selected from the group consisting of Pt and Au.
 12. Theproduct of claim 1, wherein the product is a carbonization product of acarbonaceous material with water, a water-soluble organic binder, and ametal precursor selected from the group consisting of a metal carbonate,a metal oxide, a metal hydroxide, a salt of a metal acid, a heteropolyacid, a metal carboxylate, a metal carbide, a metal chloride, a metalamine complex-containing compound, a hydrate thereof, and a mixture ofany two or more thereof.
 13. The product of claim 12, wherein thecarbonaceous material comprises a carbon black.
 14. The product of claim12, wherein the carbonaceous material comprises an activated carbon. 15.The product of claim 12, wherein the carbonaceous material comprises agraphite.
 16. The product of claim 12, wherein the carbonaceous materialis a mixture of any two or more materials selected from the groupconsisting of a carbon black, an activated carbon, and a graphite. 17.The product of claim 1, wherein the product exhibits a radial piececrush strength of greater than about 4.4 N/mm (1 lb/mm).
 18. The productof claim 1, wherein the product comprises a BET specific surface area inthe range of from about 20 m²/g to about 500 m²/g and a specific porevolume of pores having a diameter in the range of from 1.7 nm to 100 nm,as measured by the BJH process, that is from about 0.1 cm³/g to about1.5 cm³/g.
 19. A process for producing a dicarboxylic acid from analdaric acid, or salt, ester, or lactone thereof, the processcomprising: contacting the aldaric acid, or salt, ester or lactonethereof with hydrogen in the presence of a halogen-containing compoundand a hydrodeoxygenation catalyst comprising the porous, shapedmetal-carbon product of claim 1 to form the dicarboxylic acid.
 20. Theprocess of claim 19, wherein the porous, shaped metal-carbon productfurther comprises a noble metal deposited thereon.